JP2019537618A - Dibenzo [d, b] silole-based reactive mesogen - Google Patents

Abstract

Silafluorene-based reactive mesogen. The present invention provides a compound of formula (I). D-S1-A-S2-B1, Formula (I) wherein A is independently 1-20 aromatics selected from the group consisting of an aromatic moiety, a heteroaromatic moiety, and an E moiety Represents a conjugated chain of moieties, wherein A contains at least one E moiety, where E is a dibenzo [d, b] silole moiety of the following structure: E1, a moiety of the following structure: E2, And E3, which is part of the following structure: wherein E is S1 or S in the conjugated chain of A and optionally via a covalent bond at Y and Z. And each R is independently selected from the group consisting of linear or branched C1-C20 alkyl and C2-C20 alkenyl, and optionally 1-5 CH2. Groups are each replaced by oxygen, provided that acetal, ketal, per The oxide or vinyl ether is not present in the R groups, and optionally each H attached to C in each R group may be independently substituted with halogen, and the X moiety may be the same. Is selected from the group consisting of hydrogen, linear or branched C1-C8 alkyl, linear or branched C1-C8 alkoxyl, and halogen, wherein each E moiety is the same or different X moiety W is either an oxygen atom or a sulfur atom, D represents a moiety having one or more crosslinkable functional groups, S1 and S2 are flexible linker groups, B1 represents a moiety having one or more crosslinkable functional groups or a hydrogen atom, provided that when B1 represents a hydrogen atom, D represents a moiety having at least two crosslinkable functional groups. [Selection diagram] FIG.

Description

  The present invention relates to novel compounds with electronic and optoelectronic properties that make them useful for the production of electrical devices. The invention further relates to electronic devices incorporating layers containing these compounds, which compounds function as charge transporting or brilliant and electroluminescent materials.

  Organic light emitting diodes (OLEDs) are light emitting diodes in which the luminescent electroluminescent material is a film of an organic material that emits light in response to current. The luminescent organic layer of the OLED is sandwiched between two electrical contact layers. To increase efficiency, in addition to the emissive layer, the OLED device can incorporate a layer of charge transport material between the emissive layer and the electrical contact layer. These charge transport layers can include either holes or charge transport materials. These charge transport materials allow holes and electrons to migrate to the emissive layer, thereby facilitating their combination to form a bound state called an exciton. These excitons, in the case of OLED devices, eventually relax to a lower energy ground state by emitting radiation whose wavelength is often in the visible region.

  There has been considerable ongoing interest in academia and industry directed toward the research and development of new materials with improved properties suitable for use in manufacturing OLED devices. For example, materials that function as light emitters, electron transporters, and hole transporters are of particular interest. Many materials have been developed over the years in an attempt to produce improved OLED devices, specifically devices with optimal light output, energy efficiency, and lifetime. In addition, a further notable goal is the realization of a material that allows to simplify the device manufacturing process. Despite existing materials, there is a continuing need for materials with properties such as those identified above that have a superior combination of properties for OLED devices and other electronic device manufacturing.

Several reactive mesogens (liquid crystal materials that can be chemically polymerized into a cross-linked polymer matrix) of the following general formula are known.
B-S-A-S-B
In the formula, A represents a linear aromatic molecular core containing fluorene substituted with two alkyl groups at C-9, S represents a flexible spacer unit, and B represents a bridge such as a methacrylate group. And may be useful in the manufacture of organic electronic devices. When B represents a photocrosslinkable group, since the thin layer of these materials essentially functions as a photoresist that can be patterned into useful electronic structures by pattern exposure to light, especially UV light, This is especially true.

  Further, when the linear aromatic core A is intrinsically luminescent, these reactive mesogenic materials can be patterned into active luminescent layers in electroluminescent devices such as organic light emitting diodes (OLEDs) and organic diode lasers. can do. However, useful OLED devices with the BSASB structure have shown disappointing low lifetime or difficult low yield synthetic routes. The materials used in these BSASB structures have shown slow cure times, which increases the difficulty of device fabrication.

  OLEDs containing polymeric silafluorene are described in the literature (Chan, KL; McKiernan, MJ; Towns, CR; Holmes, ABJ Am. Chem. Soc. 2005, 127). , 7662-7663), which have been shown to exhibit improved photostability over their fluorene counterparts. Polymeric silafluorene materials that can be patterned by photolithography are also described in the literature (McDowell, JJ; Maier-Flag, F; Wolf, TJA; Unterreiner, AN; Lemmer, U.; Ozin, G. ACS Appl.Mater.Interfaces 2014, 6, 83-93). Polymer OLED materials are known to have reproducibility problems due to polydispersity and poor purity of the active polymer material.

  JP 2010 / 215759A discloses materials for organic electroluminescent devices, displays, lighting devices and organic electroluminescent devices.

  JP 2013/155294 discloses materials for organic electroluminescent devices and their use.

  WO 2015/159098 discloses fluoroalkylfluorene derivatives.

  WO 2012/098410 discloses a polymer network.

  WO 2006/058182 discloses lighting elements, devices and methods.

  WO 2005/034184 discloses lighting elements, devices and methods.

  US 2003/0119936 discloses luminescent polymers.

  An object of the present invention is to provide a novel sila for use in electronic devices that overcomes or substantially reduces the problems associated with existing fluorene derivatives, or at least provides a commercially useful alternative thereto. It is to provide a fluorene-containing material.

下記構造の部分であるＥ^２、

および下記構造の部分であるＥ^３、からなる群から選択され、

Ｅは、Ａの共役鎖中で、かつ任意選択でＹおよびＺでの共有結合を介してＳ^１またはＳ^２に結合しており、
各Ｒは、独立して、直鎖状または分枝鎖状のＣ_１〜Ｃ_２０アルキルおよびＣ_２〜Ｃ_２０アルケニルからなる群から選択され、任意選択で、１〜５個のＣＨ_２基が、それぞれ酸素で置換され、ただし、アセタール、ケタール、ペルオキシド、またはビニルエーテルは、Ｒ基には存在せず、任意選択で、各Ｒ基中のＣに結合している各Ｈは、独立してハロゲンで置換されていてもよく、
Ｘ部分は、同一であり、水素、直鎖状または分岐鎖状のＣ_１〜Ｃ_８アルキル、直鎖状または分岐鎖状のＣ_１〜Ｃ_８アルコキシル、およびハロゲンからなる群から選択され、各Ｅ部分は、同一または異なるＸ部分を有してもよく、
Ｗは、酸素原子または硫黄原子のいずれかであり、
Ｄは、１つ以上の架橋性官能基を有する部分を表し、
Ｓ^１およびＳ^２は、柔軟なリンカー基であり、
Ｂ^１は、１つ以上の架橋性官能基を有する部分または水素原子を表し、ただし、Ｂ^１が水素原子を表す場合、Ｄは、少なくとも２つの架橋性官能基を有する部分を表す、化合物。 In a first aspect of the present invention, there is provided a compound of formula (I),
^{D-S 1 -A-S 2} -B 1, formula (I)
Where:
A independently represents a conjugated chain of 1 to 30 aromatic moieties selected from the group consisting of an aromatic moiety, a heteroaromatic moiety, and an E moiety, where A is at least one E moiety Including
E is
E ¹ which is a dibenzo [d, b] silole moiety having the following structure:

E ² , which is a part of the following structure,

And E ³ , which is part of the following structure:

E is attached to S ¹ or S ² in the conjugated chain of A and optionally via a covalent bond at Y and Z;
Each R is independently selected from the group consisting of linear or branched C ₁ -C ₂₀ alkyl and C ₂ -C ₂₀ alkenyl, optionally having from 1 to 5 CH ₂ groups. Each of which is substituted with oxygen, provided that the acetal, ketal, peroxide, or vinyl ether is not present in the R group, and optionally each H attached to C in each R group is independently halogen May be replaced by
The X moiety is the same and is selected from the group consisting of hydrogen, linear or branched C ₁ -C ₈ alkyl, linear or branched C ₁ -C ₈ alkoxyl, and halogen; The E moiety may have the same or different X moieties,
W is either an oxygen atom or a sulfur atom;
D represents a moiety having one or more crosslinkable functional groups,
S ¹ and S ² are flexible linker groups,
B ¹ represents a moiety having one or more crosslinkable functional groups or a hydrogen atom, provided that when B ¹ represents a hydrogen atom, D represents a moiety having at least two crosslinkable functional groups.

  The compounds of formula (I) are for use in making OLEDs. Specifically, the stability of such dibenzo [d, b] silole-containing materials (also known as silafluorene materials) is considered beneficial for OLEDs.

  By the term "aromatic / heteroaromatic moiety" as used herein is meant a single aromatic or fused ring system. Thus, the biphenyl ring system, even though fully conjugated, will represent two aromatic moieties in the chain.

By the term "chain" is meant that the aromatic / heteroaromatic moieties are connected in a row. Such moieties provided as substituents that do not extend the chain length do not count against the limit of 1 to 30 aromatic moieties. The aromatic / heteroaromatic moieties can be linked directly by a covalent bond or by an ethyne or ethene linker. Ethene or ethyne linkers can maintain chain conjugation but facilitate chain synthesis. If ethene linkers are used, they are preferably transethene. The linker structure is shown below using benzene as an exemplary aromatic moiety. Preferably, the moieties are directly linked by a covalent bond.

The aromatic / heteroaromatic moieties can be joined by intervening atoms, as long as the atoms do not interfere with the conjugation of the chain. Linker atoms (such as nitrogen atoms) in the conjugated chain can be replaced with additional aromatic or heteroaromatic groups not in the chain. As noted above, such moieties do not count against the limit of 1 to 30 aromatic moieties. Preferably, the chains do not contain any such linker atoms.

As described above, A independently represents a conjugated chain of 1 to 20 aromatic moieties selected from the group consisting of an aromatic moiety, a heteroaromatic moiety, and an E moiety, wherein A is at least Includes one E part. Each E moiety is linked in the chain via the Y and Z positions. If the E portion at the end of the chain, it is through the covalent bond at C-3 and C-7, will bind to either ^the S ¹ or S ^2.

Preferably, A has the following structure:
-Ar ^a- (E-Ar ^a ) _n-
Wherein each Ar ^a is independently a valence, a diradical containing an aromatic moiety, a diradical containing a heteroaromatic moiety, an E moiety, or 2-5 aromatics interconnected by a single bond. , A heteroaromatic, and / or a chain comprising an E moiety, wherein n is an integer from 1 to 8.

Preferably, each Ar ^a is independently a diradical comprising a C ₆ -C ₂₂ aromatic moiety, a diradical comprising a heteroaromatic moiety having 4 to ₂₂ , preferably 4 to 18 carbon atoms, an E moiety Or a chain comprising two or three aromatic, heteroaromatic, and / or E moieties interconnected by a single bond.

_Preferably, diradical containing C 6 _{-C 22} aromatic moieties, 1,3-phenylene, 1,4-phenylene, 1,4-phenylene vinylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl , 9,9-dialkylfluorene-2,7-diyl, 9,9-dialkylfluorene-3,6-diyl, 9- (1'-alkylidene) fluorene) -2,7-diyl, 1,3-xylene- 2,5-diyl, 1,4-xylene-2,5-diyl, dulen-3,6-diyl, perylene-3,10-diyl, perylene-2,8-diyl, perylene-3,9-diyl, And a diradical selected from the group consisting of pyrene-2,7-diyl and / or comprising a heteroaromatic moiety having 4 to 22 carbon atoms is 2,2′-dithiophene-5,5′-diyl, Orchid-2,5-diyl, thiophen-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,2,4,5-tetrazin-3,6-diyl, 1, 2,4-oxazole-3,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,2,5-oxadiazole-3,4-diyl, 2,5-dioxy Benzene-1,4-diyl, thieno [3,2-b] thiophene-2,5-diyl, dithieno [3,2-b: 2 ′, 3′-d] thiophene-2,6-diyl, dithieno [ 3,2-b: 2 ′, 3′-d] thiophene-3,7-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-4,6-diyl, and dibenzothiophene-2,8-diyl; Benzo [1,2-b: 4,5-b '] bis [1] benzothio Phen-3,9-diyl, thiazolo [5,4-d] thiazole-2,5-diyl, oxazolo [5,4-d] oxazole-2,5-diyl, thiazolo [5,4-d] oxazole- 2,5-diyl, thiazolo [4,5-d] thiazol-2,5-diyl, oxazolo [4,5-d] oxazole-2,5-diyl, thiazolo [4,5-d] oxazole-2, 5-diyl, 2,1,3-benzothiadiazole-4,7-diyl, 4-thien-2-yl-2,1,3-benzothiazol-7,5′-diyl, 4,7-dithien-2 -Yl-2,1,3-benzothiazole-5 ', 5''-diyl, imidazo [4,5-d] imidazole-2,5-diyl, 4-alkyl-1,2,4-triazole-3 , 5-diyl, 9-alkylcarbazole-2 , 7-diyl, 9-alkylcarbazole-3,6-diyl, 1,7-dialkylindolo [2,3-b] carbazole-3,9-diyl, 1,7-dialkylindolo [2,3- b] carbazole-2,8-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-4,11-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-5 12-diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-3,9-diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-4,10-diyl, Benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl, benzo [1,2-b: 5,4-b'] dithiophen-2,6-diyl, [1] benzothieno [3,2-b] [1] benzothiophene 2,7-diyl, benzo [1,2-d: 4,5-d '] bisoxazole-2,6-diyl, benzo [1,2-d: 5,4-d'] bisoxazole-2, It is selected from the group consisting of 6-diyl, and 5,5-dioxodibenzothiophene-3,7-diyl diradical. Preferably, diradical includes _C 6 _{-C 20} aromatic moiety or heteroaromatic moiety having 4 to 18 carbon atoms.

Preferably, A comprises 1 to 10 E moieties and / or A represents a conjugated chain of 8 to 16 aromatic moieties. Preferably, A contains at least three different aromatic moieties. In certain preferred embodiments, the ^{-Ar 1 - (E-Ar 2} ) n - number of E in the group is selected from 1～6,1～3,3～6 or 5 or 6,,.

またはより大きなジベンゾ［ｄ，ｂ］シロール系構造Ｅ^２、

またはＥ^３、

である。 As described above, E is, dibenzo [d, b] silole part of the structure ^{E 1,}

Or a larger dibenzo [d, b] silole-based structure E ² ,

Or E ³ ,

It is.

Each R is independently selected from the group consisting of _C 1 _{-C 20} alkyl and _C 2 _{-C 20} alkenyl, linear or branched, optionally, is 1-5 CH ₂ groups Each of which is substituted with oxygen, provided that the acetal, ketal, peroxide, or vinyl ether is not present in the R groups, and optionally each H attached to C in each R group is independently halogen May be substituted.

R group containing a C ₄ -C ₂₀ alkyl and _C 4 _{-C 20} alkenyl, preferred because the solubility is increased. Shorter chain lengths can be used with longer chain lengths of X to increase solubility. For example, when X is _C 5 -C ₈ alkyl or _alkoxyl, C 1 -C ₃ alkyl or alkenyl may be used.

In certain embodiments, R _groups contain _-CF 2 -CF 2 -R ^6, wherein, ^{R 6} _is C 1 _{-C 18} alkyl and _C 2 _{-C 18} alkenyl, optionally, 1 ５5 CH ₂ groups are each replaced by oxygen, provided that the acetal, ketal, peroxide, or vinyl ether is not present on the R groups and is optionally attached to the C in each R group Each H may be independently substituted with halogen.

Examples of such R groups are:

This structure, because it provides the advantages associated with the synthesis of the compounds, preferably, each E is E ¹ structure.

B ¹ represents a moiety having one or more crosslinkable functional groups or a hydrogen atom, provided that when B ¹ represents a hydrogen atom, D represents a moiety having at least two crosslinkable functional groups. B ¹ is hydrogen and D is
-B ² -S ³ -B ³ -S ^1a -AS ^2a -B ^{1a
-S 3 (B 2) -B 3} -S 1a -A-S 2a -B 1a
^{-S 3 (B 2) (B} 3) -S 1a -A-S 2a -B 1a
D represents a moiety having two or more crosslinkable functional groups, as in —S ³ (B ² ) (B ³ ) or —A—S ² —B ¹ .
In the formula, B ^1a represents a moiety having a crosslinkable functional group or a hydrogen atom,
B ² and B ³ each represent a moiety having a crosslinkable functional group,
S ^1a and S ^2a are flexible linker groups, and S ³ is a spacer group. When any of the foregoing moieties are present more than once in a compound, in each case they may be the same or different, ie, they are independently selected from the foregoing definitions.

  Preferably, in the portion having one or more crosslinkable functional groups, the crosslinkable functional group is selected from the group consisting of ethylene, diene, thiol, and oxetane.

Preferably, the crosslinkable moiety is selected from the group consisting of linear and cyclic α, β-unsaturated esters, α, β-unsaturated amides, vinyl ethers, and non-conjugated diene crosslinkable groups, preferably methacrylate, Consists of ethacrylate, ethyl maleate, ethyl fumarate, N-maleimide, vinyloxy, alkylvinyloxy, vinyl maleate, vinyl fumarate, N- (2-vinyloxymaleimide), and 1,4-pentadien-3-yl Selected from a group. The vinyl ether function is attached to a flexible linker or spacer (S ¹ , S ^1a , S ² , S ^2a , or S ³ ) via intervening hydrocarbyl structures such as 4-vinyloxyphenyloxy and 2-vinyloxyethyl groups. Are combined.

  Where the compounds of the present invention have only a single crosslinkable group, they will form a network polymer unless provided in combination with a second monomer (or polymer) having two or more crosslinkable groups. Cannot be formed.

  In a preferred embodiment, the polymerizable crosslinkable group is selected from the group of ethylenic, diene, thiol and oxetane polymerizable crosslinkable groups. An ethylene crosslinkable group is a crosslinkable group containing a carbon-carbon double bond. In a preferred embodiment, all crosslinkable groups independently represent an ethylene-based crosslinkable group. Preferred ethylenic crosslinkable groups include electron rich and electron deficient ethylenic crosslinkable groups.

  In a preferred embodiment, the crosslinkable group undergoes a crosslinking reaction upon radiation exposure. In a preferred embodiment, the crosslinkable group is a photocrosslinkable group, that is, a group that undergoes a crosslinking reaction upon exposure to ultraviolet (UV) light.

  Examples of preferred crosslinkable groups are linear and cyclic α, β-unsaturated esters and α, β-unsaturated amides, linear terminal alkenes, bridged cyclic alkenes, thiols, vinyl ethers, cyclic ethers and non-conjugated diene bridges. It is a sex group. Therefore, preferred crosslinkable groups are acrylates, methacrylates, monomethyl maleate, monoethyl maleate, monomethyl fumarate, monoethyl fumarate, , 4,4-trifluorocrotonate, N-maleimide, ethenyl, N-vinylpyrrolidone, N-substituted-N-vinylformamide, N-substituted-N-vinylalkylamide, norbornene, sulfhydryl, vinyloxy, methylvinyloxy, 1,3-propylene oxide (oxetane), 1,4-pentadiene, 1,6-heptadiene, and diallylamine.

上記の基は、スペーサー基Ｓ（エチル基およびフェニル基）の一部も含む架橋性基（ビニルオキシ）の例を示す。

In a preferred embodiment, the crosslinkable group is an electron rich ethylenic crosslinkable group. Electron-rich ethylenic crosslinkable groups contain an ethylene group substituted with one or more electron donating groups. The electron donating group can include a heteroatom such as O, N, or S. In a preferred embodiment, the electron-rich crosslinkable group is a vinyloxy group. Other electron-donating group-substituted crosslinkable groups include 1-alkenyl ethers such as propen-1-yloxy and buten-1-yloxy; cyclic vinyl ethers such as cyclohexen-1-yloxy and cyclopenten-1-yloxy; 2-norbornene -2-yloxy group and other bicyclic vinyl ethers. The crosslinkable group is attached to the rest of the structure via the S group.

The above group is an example of a crosslinkable group (vinyloxy) including a part of the spacer group S (ethyl group and phenyl group).

  In a preferred embodiment, the crosslinkable group is an electron-deficient ethylenic crosslinkable group. Electron deficient ethylenic crosslinkable groups contain an ethylene group substituted with one or more electron withdrawing groups. The electron withdrawing group can include a carbonyl group and can be, for example, an ester or an amide. In a preferred embodiment, the electron deficient crosslinkable group comprises a monoalkyl maleate group, a monoalkyl fumarate group, a monoaryl maleate group, a monoaryl fumarate group or a maleimide group. Other examples of electron deficient crosslinkable groups are acrylate, methacrylate, 4,4,4-trifluorocrotonate, Z- and E-3-cyanoacrylate, Z- and E-3-cyanomethacrylate, mono- Alkylcyclohexene-1,2-dicarboxylate, and monoalkylcyclopentene-1,2-dicarboxylate.

Preferably, when present, D, and B ¹ , B ² , and B ³ are radiation activated crosslinkable groups.

^{Preferably, -S 1, -S 2, -S} 1a and ^{-S 2a,} in each occurrence, is independent of the Formula II.
-K ₁ -R ₃ , formula (II)
Wherein R ₃ is a linear or branched C ₅ -C ₁₄ alkyl, optionally wherein 1 to 5 CH ₂ groups are each replaced by oxygen, provided that acetal, ketal , Peroxide, or vinyl ether is not present in the -S ¹ , -S ² , -S ^1a , or -S ^2a moieties, and K ₁ is a valence, or an ether, ester, carbonate, thioether, amine, or amide. It is a union.

Preferably, -R ₃ in each occurrence is a straight-chain _C 5 _{-C 14} alkyl, optionally 1-5 CH ₂ groups are each substituted by oxygen, however, acetal, ketal , peroxides or vinyl ethers, ^may, -S ^1, -S 2, not present in the ^{-S 1a} or ^{-S 2a} moiety.

Preferably, -S ³ in each occurrence is independent of the formula III.
—K ₂ —R ₄ , formula (II)
Wherein each R ₄ is independently 1 to 5 R ₅ moieties linked by a valence, ether or ester bond, and each R ₅ moiety is independently a linear Or a branched C ₁ -C ₂₀ alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₆ -C ₁₆ aryl group, or a C ₄ -C ₁₅ heteroaryl group, and optionally each R ₅ each H bound to C in the group may be substituted with independently halogen, K ₂ is Ataishirube or ether, ester, carbonate, thioether, amine or amide bond. The R ₅ moiety may be arranged to form a chain, or may form a branched structure with one or more of the R ₅ moieties attached with an additional K ₂ group, or, in one embodiment, If the K ₂ represents a carbon (C, CH, CH _2), or nitrogen centers _{(N, NH, NH 2)} , respectively, bind to _{K 2} parts.

In a preferred embodiment, each R group attached to Si comprises C ₄ -C ₂₀ alkyl or C ₄ -C ₂₀ alkenyl, and each spacer group —S ¹ and —S ² is ₅ -C ₁₄ includes alkyl, optionally 1-5 CH ₂ groups are each substituted by oxygen, however, acetal, ketal, peroxide or vinyl ether, is the -S ¹ or -S ² parts not exist. Flexible spacers allow the aromatic portion of the molecule to align with the liquid crystal phase.

In a preferred embodiment, each R group bonded to Si _may include C 4 _{-C 20} alkyl or _C 4 _{-C 20} alkenyl, each spacer group ^{-S 1, -S 2, -S 1a} and, - S ^2a comprises a linear C ⁵ -C ¹⁴ alkyl, wherein optionally 1 to 5 CH ₂ groups are each replaced by oxygen, provided that the acetal, ketal, peroxide or vinyl ether is- It is not present in the S ¹ , -S ² , -S ^1a , or -S ^2a portions.

  Preferably, the compound exhibits a liquid crystal order and is preferably nematic. In another embodiment, the compound exhibits a smectic phase.

  The present inventors have found that when the compound of the present invention exhibits a smectic phase, crosslinking the material while in the smectic phase can improve crosslinking efficiency.

  According to a further aspect, there is provided a network polymer formed by exposure of a compound as disclosed herein to radiation, optionally wherein said radiation is ultraviolet light.

  According to a further aspect, there is provided a device comprising one or more charge transport layers and / or luminescent layers comprising a network polymer or compound as disclosed herein.

  Preferably, the device is an OLED device, a photovoltaic device, or a thin film transistor (TFT) device.

  Preferably, the network polymers or compounds disclosed herein are provided in a hole transport layer or electron transport layer provided directly adjacent to the electron transport layer or hole transport layer, respectively.

  Preferably, the device is an OLED device having a luminescent layer, wherein the network polymer or compound forms a uniformly oriented liquid crystal structure, whereby the luminescent layer emits linearly polarized light.

  According to a further aspect, there is provided a method of forming a device as disclosed herein, the method comprising providing a layer comprising a compound disclosed herein and selectively forming a layer comprising the compound disclosed herein. Irradiating the polymer with radiation, preferably ultraviolet radiation, to form a network polymer, and washing away unirradiated unpolymerized compounds.

  Preferably, the method comprises providing a further layer comprising a compound as disclosed herein and selectively irradiating this layer with radiation, preferably ultraviolet radiation, to form a network polymer. And washing away the unpolymerized unpolymerized compound.

  According to a further aspect, there is provided an apparatus obtainable by a method disclosed herein, the apparatus comprising two or more network polymers each forming a patterned structure, wherein the structure is essentially electroluminescent. The wavelength of the electroluminescence emitted by one of the patterned structures is different from the wavelength of the electroluminescence emitted by at least one other patterned structure.

式中、Ｌｇは、ハロゲン原子またはボレート脱離基であり、好ましくはＬｇは、臭素であり、
各Ｒは、独立して、直鎖状または分枝鎖状のＣ_１〜Ｃ_２０アルキルおよびＣ_２〜Ｃ_２０アルケニルからなる群から選択され、任意選択で、１〜５個のＣＨ_２基が、それぞれ酸素で置換され、ただし、アセタール、ケタール、ペルオキシド、またはビニルエーテルは、Ｒ基には存在せず、任意選択で、各Ｒ基中のＣに結合している各Ｈは、独立してハロゲンで置換されていてもよく、
Ｘ部分は、同一であり、水素、直鎖状または分岐鎖状のＣ_１〜Ｃ_８アルキル、直鎖状または分岐鎖状のＣ_１〜Ｃ_８アルコキシル、およびハロゲンからなる群から選択され、
式ＩＶの化合物は、１つ以上のＥ^１部分を提供する。 According to a further aspect, there is provided the use of a compound according to Formula IV to synthesize a compound disclosed herein.

Wherein Lg is a halogen atom or a borate leaving group, preferably Lg is bromine;
Each R is independently selected from the group consisting of _C 1 _{-C 20} alkyl and _C 2 _{-C 20} alkenyl, linear or branched, optionally, is 1-5 CH ₂ groups Each of which is substituted with oxygen, provided that the acetal, ketal, peroxide, or vinyl ether is not present in the R group, and optionally each H attached to C in each R group is independently halogen May be replaced by
X moieties are identical, is selected from hydrogen, linear or branched C ₁ -C ₈ alkyl, linear or branched C ₁ -C ₈ alkoxyl, and halogen,
Compounds of formula IV may provide one or more E ¹ portion.

式中、Ｒ_１およびＲ_２は、独立して、Ｃ_１〜Ｃ_１２アルキル、Ｃ_６〜Ｃ_１０アリール、またはＣ_５〜Ｃ_９ヘテロアリールからなる群から独立して選択され、
Ｌ_１およびＬ_２は、独立して、脱離基、任意選択で、Ｃｌ、Ｂｒ、Ｉ、Ｏ−トシル、Ｏ−メシル、またはＯ−トリフリルから選択され、
ｍおよびｓは、それぞれ独立して、１〜１０から選択される整数であり、
合成は、フェノール性酸素を式Ｖの化合物を用いてアルキル化する工程を含み、
式Ｖの化合物は、１つ以上のＳ^３部分を提供する。 According to a further aspect, there is provided the use of a compound according to Formula V for synthesizing a compound disclosed herein.

Wherein R ₁ and R ₂ are independently selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl, or C ₅ -C ₉ heteroaryl;
L ₁ and L ₂ are independently selected from a leaving group, optionally Cl, Br, I, O-tosyl, O-mesyl, or O-trifuryl;
m and s are each independently an integer selected from 1 to 10,
The synthesis comprises alkylating phenolic oxygen with a compound of formula V,
Compounds of formula V may provide one or more S ³ parts.

  Preferably, the compound according to formula V is diethyl-2,5-di (bromohexyl) oxyterephthalate.

In this specification, especially C ₆ -C ₂₂ aromatic moiety, and chemical species Ar ^a, which may be independently selected from the diradical containing heteroaromatic moiety having 4 to 22 carbon atoms diradical is disclosed. Although various lists are provided herein, and in particular, divided into two distinct sections, a complete list of preferred embodiments follows. Phenylene-1,3-diyl, phenylene-1,4-diyl, phenylenevinylene-1,4-diyl, cyanophenylenevinylene-1,4-diyl, phenyleneethynylene-1,4-diyl, 2,5-di Alkoxybenzene-1,4-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, anthracene-9,10-diyl, 9,9-dialkylfluorene-2,7-diyl, 9,9- Dialkylfluorene-3,6-diyl, 6,12-dihydro-6,6,12,12-tetraoctyl-indeno [1,2-b] fluorene-2,8-diyl, 6,12-dihydro-6 6,12,12-tetraoctyl-indeno [1,2-b] fluorene-3,9-diyl, 9- (1′-alkylidene) fluorene) -2,7-diyl, 2 -Methylbenzene-1,4-diyl, 2,6-xylene-1,4-diyl, 2,5-xylene-1,4-diyl, 2,3-xylene-1,4-diyl, 2,3 5-trimethylbenzene-1,4-diyl, 2,3,5,6-dulene-1,4-diyl, 2-fluorobenzene-1,4-diyl, 2,6-difluorobenzene-1,4-diyl , 2,5-difluorobenzene-1,4-diyl, 2,3-difluorobenzene-1,4-diyl, 2,3,5-trifluorobenzene-1,4-diyl, 2,3,5,6 -Tetrafluorobenzene-1,4-diyl, perylene-3,10-diyl, perylene-2,8-diyl, perylene-3,9-diyl, and pyrene-2,7-diyl, 2,2'-dithiophene -5,5'-diyl, furan-2,5- Yl, thiophen-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,2,4,5-tetrazin-3,6-diyl, 1,2,4-oxazole- 3,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,2,5-oxadiazole-3,4-diyl, 2,5-dioxybenzene-1,4- Diyl, thieno [3,2-b] thiophen-2,5-diyl, dithieno [3,2-b: 2 ′, 3′-d] thiophen-2,6-diyl, dithieno [3,2-b: 2 ′, 3′-d] thiophen-3,7-diyl, dibenzothiophen-3,7-diyl, dibenzothiophen-4,6-diyl, dibenzothiophen-2,8-diyl, benzo [1,2-b : 4,5-b '] bis [1] benzothiophene-3,9-diyl Thiazolo [5,4-d] thiazol-2,5-diyl, oxazolo [5,4-d] oxazole-2,5-diyl, thiazolo [5,4-d] oxazole-2,5-diyl, thiazolo [ 4,5-d] thiazol-2,5-diyl, oxazolo [4,5-d] oxazole-2,5-diyl, thiazolo [4,5-d] oxazole-2,5-diyl, 2,1, 3-benzothiadiazole-4,7-diyl, 4-thien-2-yl-2,1,3-benzothiazole-7,5'-diyl, 9-fluorenone-2,7-diyl, 4,7-dithiene -2-yl-2,1,3-benzothiazole-5 ′, 5 ″ -diyl, 2,1,3-benzoxadiazole-4,7-diyl, imidazo [4,5-d] imidazole- 2,5-diyl, 4-alkyl-1,2 4-triazole-3,5-diyl, N-alkylcarbazole-2,7-diyl, N-alkylcarbazole-3,6-diyl, 5,11-dialkylindolo [3,2-b] carbazole-3, 9-diyl, 5,11-dialkylindolo [3,2-b] carbazole-2,8-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-4,11-diyl, 2, 9-dialkylcarbazolo [3,2-b] carbazole-5,12-diyl, 5,7-dihydroindolo [2,3-b] carbazol-2,10-diyl, 11,12-dihydroindolo [ 2,3-a] carbazole-3,8-diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-3,9-diyl, 1,7-dialkyldiindolo [3,2- b] Offen-4,10-diyl, benzo [b] benzo [4,5] thieno [2,3-d] thiophen-2,7-diyl, benzo [1,2-d: 4,5-d '] bis (Oxazole) -2,6-diyl, benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl, benzo [1,2-b: 5,4-b'] dithiophene- 2,6-diyl, [1] benzothieno [3,2-b] [1] benzothiophen-2,7-diyl, benzo [1,2-d: 4,5-d ′] bisoxazole-2,6 -Diyl, benzo [1,2-d: 5,4-d '] bisoxazole-2,6-diyl, dibenzo [b, d] thiophene-5,5-dioxide-3,7-diyl, 5,5 -Dioxodibenzothiophene-3,7-diyl, 3,4,5-triphenyl-4H-1,2,4 Triazole-4,4-diyl, benzo [d] oxazole-2,6-diyl, triphenylamine-4,4-diyl, N, N-diphenylnaphthalen-2-amine-4,4-diyl, N, N Diphenylnaphthalene-1-amine-4,4-diyldiradical.

  A preferred list is as follows: phenylene-1,4-diyl, phenylenevinylene-1,4-diyl, phenyleneethynylene-1,4-diyl, 9,9-dialkylfluorene-2,7-diyl, 9 , 9-Dialkylfluorene-3,6-diyl, 9- (1′-alkylidene) fluorene-2,7-diyl, 2,5-dialkoxybenzene-1,4-diyl, 6,12-dihydro-6 6,12,12-tetraoctyl-indeno [1,2-b] fluorene-2,8-diyl, 6,12-dihydro-6,6,12,12-tetraoctyl-indeno [1,2-b] Fluorene-3,9-diyl, 5,11-dialkylindolo [3,2-b] carbazole-3,9-diyl, 5,11-dialkylindolo [3,2-b] carbazole 2,8-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl, cyanophenylenevinylene-1,4-diyl, benzo [b] benzo [4,5] thieno [2,3-d] Thiophene-2,7-diyl, benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl, benzo [1,2-d: 4,5-d'] bis (oxazole) -2,6-diyl, dibenzo [b, d] thiophene-5,5-dioxide-3,7-diyl, 2,1,3-benzothiadiazole-4,7-diyl, 2,1,3-benzoxa Diazole-4,7-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2,4,5-tetrazin-3,6-diyl, furan-2,5-diyl, thiophene -2,5-diyl, 1,3,4-thiaasia 2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 9-fluorenone-2,7-diyl, N-alkylcarbazole-2,7-diyl, N-alkylcarbazole -3,6-diyl, 2-methylbenzene-1,4-diyl, 2,6-xylene-1,4-diyl, 2,5-xylene-1,4-diyl, 2,3-xylene-1, 4-diyl, 2,3,5-trimethylbenzene-1,4-diyl, 2,3,5,6-dulen-1,4-diyl, triphenylamine-4,4-diyl, N, N-diphenyl Naphthalen-2-amine-4,4-diyl, N, N-diphenylnaphthalen-1-amine-4,4-diyl, 2-fluorobenzene-1,4-diyl, 2,6-difluorobenzene-1,4 -Diyl, 2,5-difluorobe Benzene-1,4-diyl, 2,3-difluorobenzene-1,4-diyl, 2,3,5-trifluorobenzene-1,4-diyl, 2,3,5,6-tetrafluorobenzene-1 , 4-Diyl, 3,4,5-triphenyl-4H-1,2,4-triazole-4,4-diyl, benzo [d] oxazole-2,6-diyldi-radical.

Preferred Embodiment In the following, the term “crosslinkable group” is used as an abbreviation for the term “moiety having a crosslinkable functional group”.

  In the following, the term "connected to each other by a single bond" is used as an abbreviation for the requirement that these moieties form a conjugated chain.

In one embodiment, a compound of Formula Ia is provided. Wherein, R groups each E moieties are the same or different and are linear or branched _C. 4 to _{C 12 alkyl,} C 4 _{-C 12 haloalkyl,} C 4 _{-C 12 fluoroalkyl, C} 4 ~ Selected from the group consisting of C ₁₂ alkenyl groups, optionally one, two, or three CH ₂ groups are replaced with oxygen, provided that an acetal, ketal, peroxide, or vinyl ether is present in the R group In addition, D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, and n are further defined with respect to the compound of formula (I) As defined above.

In one embodiment, a compound of Formula Ib is provided. Wherein the R groups of each E moiety are the same or different and are linear C ₄ -C ₁₂ alkyl, C ₄ -C ₁₂ haloalkyl, C ₄ -C ₁₂ fluoroalkyl, C ₄ -C ₁₂ alkenyl groups And optionally 1, 2, or 3 CH ₂ groups are replaced by oxygen, provided that an acetal, ketal, peroxide, or vinyl ether is not present in the R group, and , D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, and n are as defined above for compounds of formula (I) As expected.

In one embodiment, a compound of Formula Ic is provided. Wherein, R groups are the same or different for each E moiety is selected from linear or branched _C. 4 to _{C 12} alkyl, and _C 4 _{-C 12} group consisting of fluoroalkyl, further ^{D, B} 1, B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, and n are as defined above for the compound of formula (I).

In one embodiment, a compound of Formula Id is provided. Wherein the R groups in each E moiety are the same or different and are selected from the group consisting of linear or branched C ₁ -C ₁₆ alkyl, preferably C ₄ -C ₁₂ alkyl, preferably C ₃ -C ₈ alkyl. Selected from or selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and further D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, and n are as defined above for compounds of formula (I).

In one embodiment, a compound of Formula Ie is provided. Wherein the R groups in each E moiety are the same or different and are selected from the group consisting of linear C ₁ -C ₁₆ alkyl, preferably C ₄ -C ₁₂ alkyl, preferably C ₃ -C ₈ alkyl, or Selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and further D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, and n are as defined above for compounds of formula (I).

  Preferably, in each of the above embodiments, each R group of each E moiety is provided as the same pair to facilitate synthesis. That is, preferably each E portion is symmetric.

In one embodiment, a compound of formula If is provided. Wherein, n is an integer from 1 to 6, further ^{D, B 1, B 2,} B 3, S 1, S 1a, S 2, S 2a, S 3, Ar 1, Ar 2, E and, R is as defined above for compounds of formula (I), (Ia), (Ib), (Ic), (Id), or (Ie).

In one embodiment, a compound of Formula Ig is provided. In the formula, n is an integer of 3 to 6, and D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, and R is as defined above for compounds of formula (I), (Ia), (Ib), (Ic), (Id), or (Ie).

In one embodiment, there is provided a compound of formula Ih. Wherein Ar ¹ and Ar ² , at each occurrence, are independently selected from Ar ^a and a group comprising ^a valence, wherein A ^a is an aromatic, heteroaromatic, or E moiety, or a single moiety. Represents a diradical containing two or three aromatic, heteroaromatic, or E moieties joined to each other by bonds, and further D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , E, R, and n are of the formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), or (Ig) As defined above for compounds.

In one embodiment, a compound of Formula Ii is provided. Wherein Ar ¹ and Ar ² , at each occurrence, are independently selected from Ar ^a and a group comprising ^a valence, wherein Ar ^a is a single aromatic, heteroaromatic, or E moiety, or a single moiety. Represents a diradical containing two or three aromatic, heteroaromatic, or E moieties linked together by bonds, wherein the aromatic, heteroaromatic moieties are, independently at each occurrence, 1,3 -Phenylene, 1,4-phenylene, 1,4-phenylenevinylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, 9,9-dialkylfluorene-2,7-diyl, 9,9-dialkyl Fluorene-3,6-diyl, 9- (1′-alkylidene) fluorene) -2,7-diyl, 1,3-xylene-2,5-diyl, 1,4-xylene-2,5-diyl, durene − , 6-Diyl, perylene-3,10-diyl, perylene-2,8-diyl, perylene-3,9-diyl, and pyrene-2,7-diyl, 2,2'-dithiophene-5,5'- Diyl, furan-2,5-diyl, thiophen-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,2,4,5-tetrazine-3,6-diyl, 1,2,4-oxazole-3,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,2,5-oxadiazole-3,4-diyl, 2,5- Dioxybenzene-1,4-diyl, thieno [3,2-b] thiophene-2,5-diyl, dithieno [3,2-b: 2 ′, 3′-d] thiophene-2,6-diyl, Dithieno [3,2-b: 2 ′, 3′-d] thiophene-3,7-diyl, Benzothiophene-3,7-diyl, dibenzothiophene-4,6-diyl, and dibenzothiophene-2,8-diyl, benzo [1,2-b: 4,5-b '] bis [1] benzothiophene- 3,9-diyl, thiazolo [5,4-d] thiazol-2,5-diyl, oxazolo [5,4-d] oxazole-2,5-diyl, thiazolo [5,4-d] oxazole-2, 5-diyl, thiazolo [4,5-d] thiazole-2,5-diyl, oxazolo [4,5-d] oxazole-2,5-diyl, thiazolo [4,5-d] oxazole-2,5- Diyl, 2,1,3-benzothiadiazole-4,7-diyl, 4-thien-2-yl-2,1,3-benzothiazol-7,5′-diyl, 4,7-dithien-2-yl -2,1,3-benzo Azole-5 ′, 5 ″ -diyl, imidazo [4,5-d] imidazole-2,5-diyl, 4-alkyl-1,2,4-triazole-3,5-diyl, 9-alkylcarbazole- 2,7-diyl, 9-alkylcarbazole-3,6-diyl, 1,7-dialkylindolo [2,3-b] carbazole-3,9-diyl, 1,7-dialkylindolo [2,3 -B] carbazole-2,8-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-4,11-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-5 , 12-Diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-3,9-diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-4,10-diyl , Benzo [1,2- b: 4,5-b '] dithiophen-2,6-diyl, benzo [1,2-b: 5,4-b'] dithiophen-2,6-diyl, [1] benzothieno [3,2-b ] [1] benzothiophene-2,7-diyl, benzo [1,2-d: 4,5-d '] bisoxazole-2,6-diyl, benzo [1,2-d: 5,4-d '] Bisoxazole-2,6-diyl and 5,5-dioxodibenzothiophene-3,7-diyl diradical, and further D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , E, R, and n represent the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (Ie), As defined above for compounds of Ig).

In one embodiment (eg, an embodiment in which the compound is used as a hole transport material), a compound of Formula Ij is provided. Wherein Ar ¹ and Ar ² , at each occurrence, are independently selected from Ar ^a and a group comprising ^a valence, wherein Ar ^a is a single aromatic, heteroaromatic, or E moiety, or a single moiety. Represents a diradical containing two or three aromatic, heteroaromatic, or E moieties linked together by bonds, wherein the aromatic, heteroaromatic moieties are, independently at each occurrence, 1,3 -Phenylene, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, 1,3-xylene-2,5-diyl, 1,4-xylene-2,5-diyl, durene -3,6-diyl, thiophene-2,5-diyl, perylene-3,10-diyl, pyrene-2,7-diyl, perylene-2,8-diyl, perylene-3,9-diyl, 2,2 '-Dithiophene-5 '-Diyl, thieno [3,2-b] thiophene-2,5-diyl, dithieno [3,2-b: 2', 3'-d] thiophene-2,6-diyl, dibenzothiophene-3,7 -Diyl, benzo [1,2-b: 4,5-b '] bis [1] benzothiophene-3,9-diyl, 9-alkylcarbazole-2,7-diyl, 9-alkylcarbazole-3,6 -Diyl, 1,7-dialkylindolo [2,3-b] carbazole-3,9-diyl, 1,7-dialkylindolo [2,3-b] carbazole-2,8-diyl, 2,9 -Dialkylcarbazolo [3,2-b] carbazole-4,11-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-5,12-diyl, benzo [1,2-b: 4 , 5-b '] dithiophene-2,6-dii Benzo [1,2-b: 5,4-b '] dithiophen-2,6-diyl, or [1] benzothieno [3,2-b] [1] benzothiophen-2,7-diyl diradical D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , E, R, and n are selected from the formulas (I), (Ia), ( As defined above for compounds of Ib), (Ic), (Id), (Ie), (If), or (Ig).

In one embodiment (eg, an embodiment in which the compound is used as an electron transport material), a compound of Formula Ik is provided. Wherein Ar ¹ and Ar ² , at each occurrence, are independently selected from Ar ^a and a group comprising ^a valence, wherein Ar ^a is a single aromatic, heteroaromatic, or E moiety, or a single moiety. Represents a diradical containing two or three aromatic, heteroaromatic, or E moieties linked together by bonds, wherein the aromatic, heteroaromatic moieties are, independently at each occurrence, 1,3 -Phenylene, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, perylene-3,10-diyl, perylene-2,8-diyl, perylene -3,9-diyl, pyrene-2,7-diyl, oxazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, oxazolo [4,5-d] oxazole-2 , 5 -Diyl, oxazolo [5,4-d] oxazole-2,5-diyl, 4-alkyl-1,2,4-triazole-3,5-diyl, imidazo [4,5-d] imidazole-2,5 -Diyl, benzo [1,2-d: 4,5-d '] bisoxazole-2,6-diyl, benzo [1,2-d: 5,4-d'] bisoxazole-2,6-diyl Or 5,5-dioxodibenzothiophene-3,7-diyl diradical, and further D, B ¹ , B ² , B ³ , S ¹ , S ^1a , S ² , S ^2a , S ³ , E, R, and n are as defined above for compounds of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), or (Ig). It is on the street.

In one embodiment, a compound of Formula Il is provided. ^Wherein S ¹ , S ^1a , S ² , and S ^2a , in each ^occurrence, are independently selected from linear or branched C ₅ -C ₁₄ alkyl groups; Two, three, four, or five methylene groups are replaced with oxygen atoms, provided that no acetals, ketals, or peroxides are present, and any valence or ether, ester, carbonate, thioether, amine, or amide linkage. Through a bond or via a valence or ether, ester, carbonate, thioether, amine or amide bond, as determined by the nature of D, D, B ¹ , B ² , B ³ , or S ³ , and D, B ¹ , B ² , B ³ , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by formulas (I), (Ia), (Ib) ) (Ic), are as defined above for the compounds of (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), or (Ik).

In one embodiment, a compound of Formula Im is provided. ^Wherein S ¹ , S ^1a , S ² , and S ^2a , in each ^occurrence, are independently selected from linear or branched C ₅ -C ₁₄ alkyl groups; Two, three, four, or five methylene groups are replaced with an oxygen atom, provided that no acetals, ketals, or peroxides are present, and either via a valence or ether, ester, or carbonate linkage, A, and via a valence or ether, ester, or carbonate linkage to D, B ¹ , B ² , B ³ , or S ³ as determined by the nature of D; B ¹ , B ² , B ³ , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie) , (If), (Ig), (Ih), (I ), It is as defined above for the compounds of (Ij), or (Ik).

In one embodiment, a compound of formula In is provided. ^Wherein S ¹ , S ^1a , S ² , and S ^2a , at each ^occurrence, are independently selected from linear or branched C ₇ -C ₁₂ alkyl groups; Three or four methylene groups are replaced with an oxygen atom, provided that no acetals, ketals or peroxides are formed, and either via a valence or ether, ester, carbonate, thioether, amine or amide linkage , A and via a valence, ether, ester, carbonate, thioether, amine or amide bond to D, B ¹ , B ² , B ³ , or S ³ as determined by the nature of D And D, B ¹ , B ² , B ³ , S ³ , Ar ¹ , Ar ² , E, R, and n have the formulas (I), (Ia), (Ib), (Ic), (I Id) (Ie), are as defined above for the compounds of (If), (Ig), (Ih), (Ii), (Ij), or (Ik).

In one embodiment, a compound of Formula Io is provided. ^Wherein S ¹ , S ^1a , S ² , and S ^2a , in each ^occurrence, are independently selected from linear or branched C ₇ -C ₁₂ alkyl groups; Two, three, or four methylene groups are replaced with oxygen atoms, except that no acetals, ketals, or peroxides are formed, and A is converted to A via either a valence or ether, ester, or carbonate linkage. And D, B ¹ , B ² , B ³ , or S ³ , as determined by the nature of D, via a valence or ether, ester, or carbonate linkage, and further D, B ¹ , B ² , B ³ , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), ( If), (Ig), (Ih), (Ii) It is as defined above for the compounds of (Ij), or (Ik).

In one embodiment, a compound of Formula Ip is provided. Wherein B ¹ , B ² , B ³ , and D, when representing a crosslinkable group, in each occurrence independently represent a radiation activated crosslinkable group, optionally a photopolymerizable crosslinkable group; Further, S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, R and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id) , (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In), or (Io). As defined.

In one embodiment, a compound of Formula Iq is provided. In the formula, when B ¹ , B ² , B ³ , and D represent a crosslinkable group, at each occurrence, they are selected from groups containing an alkene crosslinkable group, and further, S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig) , (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In), or (Io).

In one embodiment, a compound of formula Ir is provided. Wherein B ¹ , B ² , B ³ , and D, when representing a crosslinkable group, in each occurrence independently represent an electron-rich and electron-deficient alkene crosslinkable group, and further include S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If) ), (Ig), (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In), or (Io).

In one embodiment, a compound of formula Is is provided. In the formula, when B ¹ , B ² , B ³ , and D each represent a crosslinkable group, each occurrence independently represents a photopolymerizable alkene crosslinkable group, and further, S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), As defined above for compounds of (Ig), (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In), or (Io).

In one embodiment, a compound of Formula It is provided. In the formula, B ¹ , B ² , B ³ , and D each independently represent a linear or cyclic α, β-unsaturated ester, α, β-unsaturated when each represents a crosslinkable group. Represents an alkene crosslinkable group selected from the group consisting of amides, vinyl ethers, and non-conjugated dienes, and further, S ¹ , S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, R, and n are , Formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), As defined above for compounds of (IL), (Im), (In) or (Io).

In one embodiment, a compound of Formula Iu is provided. In the formula, when B ¹ , B ² , B ³ , and D represent a crosslinkable group, in each occurrence, independently, methacrylate, ethacrylate, ethyl maleate, ethyl fumarate, N-maleimide, vinyloxy, alkyl vinyloxy, vinyl maleate, vinyl fumarate, N-(2-vinyloxy-maleimide), and 1,4-pentadiene-3-yl represents alkene crosslinkable groups selected from the group consisting of groups, further ^S 1, S ^1a , S ² , S ^2a , S ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), and (Ie). , (If), (Ig), (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In) or (Io) as defined above for a compound It is.

In one embodiment, there is provided a compound of formula Iv. In the formula, S ³ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ haloalkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₆ -C ₁₆ aryl group, or a C ₄ -C ₁₅ heteroaryl group. Or, independently of each other, 1, 2, 3, 4, or 5 C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₃ -C linked by a valence, ether or ester bond. Represents a chain consisting of C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, and / or C ₄ -C ₁₅ heteroaryl moieties, wherein S ¹ , S ^1a , S ² , S ^2a , D, B ¹ , B ² , B ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ig) Ih), (Ii), (Ij), (Ik) , (IL), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), or (Iu) as defined above. It is.

In one embodiment, there is provided a compound of formula Iw. In the formula, S ³ is a C ₁ -C ₁₄ alkyl group, a C ₁ -C ₁₄ haloalkyl group, a C ₅ -C ₆ cycloalkyl group, a C ₆ -C ₁₄ aryl group, or each independently a valence, an ether bond or are linked by an ester bond, 1, 2, 3, 4 _C 1 _{-C 14 alkyl,} C 1 _{-C 14 haloalkyl,} C 3 -C ₈ cycloalkyl, and / or _{C 6} or 5, Represents a chain consisting of -C ₁₄ aryl moieties, wherein S ¹ , S ^1a , S ² , S ^2a , D, B ¹ , B ² , B ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formula ( I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (IL) , (Im), (In), (Io), (Ip), (Iq), (Ir) ), (Is), (It), or (Iu).

In one embodiment, a compound of Formula Ix is provided. In the formula, S ³ is a C ₂ -C ₁₀ alkyl group, a C ₂ -C ₁₀ haloalkyl group, a C ₅ -C ₆ cycloalkyl group, a C ₆ -C ₁₄ aryl group, or each independently a valence, an ether 1, 2, 3, 4, or 5 C ₁ -C ₁₄ alkyl, C ₂ -C ₁₀ haloalkyl, C ₃ -C ₈ cycloalkyl, and / or C ₆ linked by a bond or an ester bond. Represents a chain consisting of -C ₁₄ aryl moieties, wherein S ¹ , S ^1a , S ² , S ^2a , D, B ¹ , B ² , B ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formula ( I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (IL) , (Im), (In), (Io), (Ip), (Iq), (Ir) ), (Is), (It), or (Iu).

In one embodiment, there is provided a compound of formula Iy. In the formula, S ³ represents a group consisting of three C ₂ -C ₁₂ alkyl groups and two C ₆ -C ₁₆ aryl groups mutually bonded by a valence, an ether bond or an ester bond. And each C ₆ -C ₁₆ aryl group is represented by i) a C ₂ -C ₁₂ alkyl group to a second C ₆ -C ₁₆ aryl group, and ii) a C ₂ -C ₁₂ alkyl group by a crosslinker B ² or B ³ and iii) bonded directly to S ¹ and S ^1a , and S ¹ , S ^1a , S ² , S ^2a , D, B ¹ , B ² , B ³ , Ar ¹ , Ar ² , E, R, and n represents the formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik) ), (IL), (Im), (In), (Io), (Ip), (Iq), (Ir), (I ), It is as defined above for the compounds of (It) or (Iu).

In one embodiment, there is provided a compound of formula Iz. Wherein S ³ consists of four C ₂ -C ₁₂ alkyl groups linked to a central C ₆ -C ₁₆ aryl group, linked together by a valence, ether or ester bond. A terminal of each independent C ₂ -C ₁₂ alkyl group that is not bonded to a central C ₆ -C ₁₆ aryl group and terminates by bonding to B ² , B ³ , S ¹ , and S ^1a , S ¹ , S ^1a , S ² , S ^2a , D, B ¹ , B ² , B ³ , Ar ¹ , Ar ² , E, R, and n are represented by the formulas (I), (Ia), (Ib) , (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In), (In) Io), (Ip), (Iq), (Ir), (Is), (It), or (Iu) It is as was.

  In one embodiment, the formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (IL), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv), (Iw) ), (Ix), (Iy), or (Iz).

  In one embodiment, formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih) for use in manufacturing OLED devices. ), (Ii), (Ij), (Ik), (IL), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), Compounds having a structure according to (Iu), (Iv), (Iw), (Ix), (Iy), or (Iz) are provided.

  The foregoing compounds can be used in a network polymer or device as described herein. Preferably, the compounds are used for OLED devices in the emissive layer. Alternatively, the compounds can be used as devices or as crosslinked network polymers in devices in the charge transport layer.

  In devices that include an interface between a hole transport layer and an electron transport layer, preferably either or both of the layers include a compound as described herein. Preferably, such a device is a photovoltaic device or a thin film transistor (TFT) device.

  Preferably, the device contains a plurality of layers comprising a compound as described herein, each layer being formed (or obtainable) by an iterative sequential deposition and in situ polymerization process.

  Preferably, the device comprises a plurality of patterned structures created (or obtained) by exposing a plurality of layers of the material comprising the compound. The device can be made using a patterned area of radiation, such as ultraviolet light, which polymerizes the material layer and then rinses away the unexposed and unpolymerized material.

  In one embodiment, an apparatus is provided that contains two or more of the above-described patterned structures, wherein the structures are comprised of a material that is inherently electroluminescent, and the electroluminescence emitted by the one patterned structure is provided. Is different from the wavelength of the electroluminescence emitted by at least one other patterned structure.

  In one embodiment, a multi-color dot matrix display is provided that includes multiple pixels of multiple colors, each pixel including one or more of the above-described patterned structures.

  In one embodiment, there is provided an apparatus containing two or more of the above-described patterned structures, wherein the structure is comprised of a material that is essentially electroluminescent and comprises two or more of the above-described patterned structures. One or more are covered in a stack, and the electroluminescent wavelengths of two or more of the patterned structures of each stack are different.

  The compounds disclosed herein can be useful in electronic devices as polymerized liquid crystal materials or as glasses formed by cooling the polymerized liquid crystal materials. Preferably, the liquid crystal material exhibits smectic and nematic mesophases.

  We have found that it is possible to "fix" a nematic liquid crystal structure by exposing a liquid crystalline fluid containing a compound as described herein to radiation, preferably ultraviolet light. Was.

  In an alternative embodiment, we can "fix" the smectic liquid crystal structure by exposing a liquid crystalline fluid containing a compound as described herein to radiation, preferably ultraviolet light. I found that it is possible. We have found that the compounds disclosed herein, when in the smectic phase, can exhibit greater cross-linking efficiencies than would otherwise be expected. This offers advantages in terms of processing efficiency when producing devices containing the compound.

  In one embodiment, an emissive layer is provided that is produced by exposing a material comprising a uniformly aligned liquid crystal structure containing a compound as disclosed herein to radiation. Such a layer can emit linearly polarized light.

  In one embodiment, a patterned polarized light-emitting structure is provided, which is produced by exposing a material comprising a uniformly oriented liquid crystal structure containing a compound as disclosed herein to a patterned area of radiation. You.

  In one embodiment, there is provided an apparatus comprising two or more of the patterned polarized light emitting structures described above, wherein at least the first polarized light emitting structure is not oriented with the polarization axis of at least the second polarized light emitting structure. It has an emission polarization axis.

  In one embodiment, a uniformly oriented liquid crystal fluid containing a crosslinkable monomer, as described herein, or an orientation of a glass formed upon cooling of the uniformly oriented liquid crystal fluid. The sequential deposition of the layers provides a 3D display that is (or can be) obtained. Such displays sequentially polymerize the patterned area of each layer in turn, and then wash out the unpolymerized area of each layer in turn, providing a light emitting structure, and thus the liquid crystal alignment, and the polarization axis of the light emission of each layer. In a direction different from the polarization axis of the light emission in each adjacent layer.

  In one embodiment, there is provided an OLED device comprising a network polymer as disclosed herein as a luminescent dopant in a host material having a liquid crystal structure.

According to one aspect of the present invention, group ^{D, B 1, S 1,} S 2 and A is a chemical group as defined herein, of formula ^{D-S 1 -A-S 2} -B 1 Compounds are provided. A represents a group of the formula -Ar ^1- (E-Ar ² ) _n- . The component parts of the system are connected to one another via a covalent bond.

When E is E ^1, this group can be represented as a compound of formula 1.

As a result, the present invention allows a better understanding of the nature of the constituent groups, and their functions are defined herein.

式中、各Ｅ部分のＸ基は同一であり、水素、直鎖状または分岐鎖状のＣ_１〜Ｃ_８アルキル、直鎖状または分岐鎖状のＣ_１〜Ｃ_８アルコキシル、およびハロゲンから選択され、ＹおよびＺでの共有結合を介して鎖に組み込まれる。 The compounds of the present invention, -Ar 1 abbreviated as ^{A - (E-Ar 2)} n - comprises a group which forms an aromatic core "substantially linear" or "lathe-like" compounds I do. In one embodiment, E is a silafluorange radical having the structure:

Wherein the X groups in each E moiety are the same and are selected from hydrogen, linear or branched C ₁ -C ₈ alkyl, linear or branched C ₁ -C ₈ alkoxyl, and halogen. And incorporated into the chain via a covalent bond at Y and Z.

および
Ｅ^３：

式中、Ｗは、酸素原子または硫黄原子のいずれかであり、それはＹおよびＺでの共有結合を介して、分子の残りの部分に組み込まれる。 In another embodiment, E is a fused silafluorene unit consisting of multiple fused pentacyclic and / or hexacyclic arenes.
E ^2:

And E ³ :

Wherein W is either an oxygen or sulfur atom, which is incorporated into the rest of the molecule via a covalent bond at Y and Z.

The integer n in —Ar ¹ — (E—Ar ² ) _n — is preferably 1 to 8. Each -Ar ^1- (E-Ar ² ) _n -group in total preferably comprises 1 to 8 E groups. In certain preferred embodiments, the ^{-Ar 1 - (E-Ar 2} ) n - number of E in the group is selected from 1～6,1～3,3～6 or 5 or 6,,.

  Surprisingly, the inventors have found that the compounds disclosed herein exhibit a broader liquid crystal range compared to conventional materials. That is, the temperature range of the liquid crystal phase of the molecule is wider than that of a conventional material such as a fluorene-based material. Advantageously, the wider liquid crystal range offers processing advantages when producing devices comprising the compounds described herein.

  The present inventors have found that the silicon-containing molecules of the present invention are cheaper and easier to synthesize than prior art compounds, and specifically, the silicon-containing molecules of the present invention are less expensive than fluoroalkylfluorene-based materials. It was found that the synthesis was easy.

  In addition, the inventors have also found that these compounds have improved photocrosslinking efficiency, and improved photocrosslinking efficiency of crosslinked and non-crosslinkable blue-emitting materials as compared to similar n-alkylfluorene-based materials. It has been found that the CIE (x, y) coordinates are also shown.

The compounds of the present invention, in a preferred embodiment is suitable for use as emitters, each ^{-Ar 1 - (E-Ar 2} ) n - group includes E group between 3-6. This is because lower n values result in molecules with lower luminous efficiency. Further small increases in energy efficiency can be achieved by further increasing the molecular core to n = 7 or 8, but the increased efficiency must be balanced with the increased cost of synthesizing such molecules. Must. In embodiments where the compounds of the present invention are suitable for use as a hole transporter, electron transporter, or host for a luminescent dopant, -Ar1- (E- having ¹ to 3 E groups. Ar ² ) _n -groups are preferred because of their ease of synthesis, lower melting points, and higher solubility.

In this -Ar ^1- (E-Ar ² ) _n- , or A structure, where n is greater than 1, each individual R group of E may represent a plurality of possible isomers of the material making purification difficult. Is the same for For n = 1 materials having different R groups in different E groups, this may be advantageous as it may lower the melting point. The R group is selected from linear or branched C ₁ -C ₁₆ alkyl, C ₁ -C ₁₆ haloalkyl, C ₁ -C ₁₆ fluoroalkyl, C ₂ -C ₁₆ alkenyl groups, and optionally 1 Each of 2, 3, 4, or 5 CH ₂ groups is replaced with oxygen, except that no acetal, ketal, peroxide, or vinyl ether is present. In other words, if more than one methylene group is replaced by an oxygen atom, it will be separated from the next oxygen atom in the chain by at least three covalent bonds. When the R group is an alkenyl group, the alkene is preferably cis and located towards the center of the hydrocarbon, which will reduce the viscosity of the product and consequently the glass transition temperature.

Ar ¹ and Ar ² , at each occurrence, are independently selected from the group comprising Ar ^a and the valence. Ar ^a include one aromatic, heteroaromatic, or E moiety or a single bond 2,3,4 or 5 aromatic coupled to each other by, a heteroaromatic and / or E moiety Represents a diradical.

The entire Ar ^1- (E-Ar ² ) _n chain is preferably “substantially linear”, destroying its linearity or its ability to align with adjacent molecules and promote liquid crystallinity. There are no significant branches to be taken. Certain elements of the chain may protrude from the linear structure. For example, if Ar ¹ is naphthalene-1,4-diyl, 5-8 carbons protrude from the side of the chain, even though the naphthyl structure is integral to the chain. Although the chain is described as entirely linear, the nature of the chemical bonds joining the component parts of the chain requires that all chemical bonds in the chain will not be correctly oriented. Can be understood. Said curvature is acceptable as long as any curvature of the skeleton of the molecular core of the material molecules does not destroy the liquid crystalline properties of the material or at least its ability to be oriented by the liquid crystal molecules. Similarly, branches that preserve the liquid crystal properties of the material are also possible.

R
The R groups are selected from linear or branched C ₁ -C ₁₆ alkyl, C ₁ -C ₁₆ haloalkyl, C ₁ -C ₁₆ fluoroalkyl, C ₂ -C ₁₆ alkenyl groups, and optionally 1 _Two , three, four, or five methylene (CH ₂ ) groups are replaced with oxygen, except that no acetal, ketal, peroxide, or vinyl ether is present. In other words, if more than one methylene group is replaced by an oxygen atom, it will be separated from the next oxygen atom in the chain by at least three covalent bonds, and the oxygen atom will, via a single bond, Not bonded to a carbon-carbon double bond. In some embodiments, the R groups for each individual E are the same. In another embodiment, all E R groups in the chain are the same.

In a preferred embodiment, R groups each E moieties are the same, linear or branched _C 4 _{-C 12 alkyl,} C 4 _{-C 12 haloalkyl,} C 4 _{-C 12 fluoroalkyl,} C 4 _{-C 12} is selected from the group consisting of alkenyl groups, optionally, two or three CH ₂ groups may be replaced, are replaced by oxygen, however, acetal, ketal or peroxide does not exist.

  In a preferred embodiment, the R groups are alkenyl groups. Alkenyl groups contain a carbon-carbon double bond. Preferred alkenyl groups contain only one carbon-carbon double bond. In a preferred embodiment, when the R group is an alkenyl group, it is a central and cis carbon-carbon double bond. In a preferred embodiment, the cis alkene is of the formula -CH = CH-.

  By the term "center" is meant that the R group is not at a terminal position, preferably substantially at the center of the chain, and has been removed from the end of the chain. For example, in a chain of 9 carbon atoms, the R group would be between 4 and 6 inclusive (i.e. 4-5 or 5-6).

As noted above, in some cases, one, two, three, four, or five methylene groups in the R group can be replaced with an oxygen atom. In this case, the R groups are ethers or polyethers. Methylene group. CH ₂ group. If more than one methylene group is replaced by an oxygen atom, there are at least two carbon atoms in the chain between them. Further, the oxygen atom is not connected to the carbon-carbon double bond via a single bond. This is because peroxide, ketal, acetal, and vinyl ether units are potentially unstable and therefore are not included in the structure of the compounds of the present invention.

Changing the length of the R group is useful because it can control the melting point of the compound. For example, if a liquid crystal compound is required, it is advantageous to use an R group having 4 to 16 carbon and oxygen atoms in the chain, since C ₁ -alkyl derivatives often exhibit a high melting point. Can be In a preferred embodiment, the R groups contain between 6 and 12 carbon and oxygen atoms in the chain.

  The introduction of an oxygen atom into the R group can advantageously be used to control the temperature at which the compound undergoes its glass transition and / or liquid crystal transition temperature, which is useful when a glassy material is required. May be advantageous to

  The introduction of carbon-carbon double bonds can be used advantageously to reduce the viscosity of the material, which is of particular interest for compounds to be solution-processed. Introducing a cis carbon-carbon double bond towards the center of the chain is particularly advantageous for adjusting the viscosity and liquid crystal transition temperature of the material.

Selected examples of E structures with fully derived R groups are provided below.

In certain embodiments, R groups _{include -CF} 2 -CF 2 -R ^6. Wherein R ⁶ is C ₁ -C ₁₈ alkyl and C ₂ -C ₁₈ alkenyl, and optionally 1 to 5 CH ₂ groups are each replaced by oxygen, provided that acetal, ketal, peroxide Or a vinyl ether is not present in the R groups, and optionally each H attached to C in each R group may be independently substituted with halogen.

化合物の構造

またはそれらのＥ^２およびＥ^３等価物は、
それらの合成有用性のために、それらのシラフルオレン誘導体発光体コアを含有する化合物の合成のための好ましい中間体である。 Examples of such R groups are:

Compound structure

Or their E ² and E ³ equivalents are
Due to their synthetic utility, they are preferred intermediates for the synthesis of compounds containing their silafluorene derivative illuminant core.

Ar ¹ and Ar ²
Ar ¹ and Ar ² , at each occurrence, are independently selected from the group comprising Ar ^a and the valence. Ar ^a include one aromatic, heteroaromatic, or E moiety or a single bond 2,3,4 or 5 aromatic coupled to each other by, a heteroaromatic and / or E moiety Represents a diradical. A diradical is a group covalently linked to two other moieties within the overall compound structure, some typical examples are shown below. “|” Indicates a typical binding site.

  In the above structure, the R groups are selected as described for the E moiety.

The exact nature of the Ar ^a group selected will depend on the properties desired in the system. For example, if a luminescent compound is required, 2, 3, 4, 5, or 6 consecutive E groups can be characterized in the structure. Alternatively, ^a high proportion of Ar groups, for example 50% or more, may be E groups.

The constituent aromatic and heteroaromatic groups composed of Ar ^a are selected from the group consisting of C ₆ -C ₁₆ aromatic groups and C ₄ -C ₁₂ heteroaromatics which may have a substituent. Can be. Optional substituents, branched or branched or be unbranched C ₁ -C ₁₀ alkyl may be selected from the group of C4~C10 heteroaromatic group or an ether group.

Useful aromatic diradicals as Ar ^a structural unit of the material of the present invention, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, thiophene-2,5-diyl, pyrimidine -2,5-diyl, pyridine-2,5-diyl, perylene-3,10-diyl, pyrene-2,7-diyl, 2,2'-dithiophen-5,5'-diyl, oxazole-2,5 -Diyl, 1,3,4-oxadiazole-2,5-diyl, thieno [3,2-b] thiophene-2,5-diyl, dithieno [3,2-b: 2 ′, 3′-d ] Thiophen-2,6-diyl, dibenzothiophen-3,7-diyl, benzo [1,2-b: 4,5-b '] bis [1] benzothiophen-3,9-diyl, thiazolo [5 4-d] thiazole-2,5-diyl Oxazolo [5,4-d] oxazole-2,5-diyl, thiazolo [5,4-d] oxazole-2,5-diyl, thiazolo [4,5-d] thiazol-2,5-diyl, oxazolo [ 4,5-d] oxazole-2,5-diyl, thiazolo [4,5-d] oxazole-2,5-diyl, 2,1,3-benzothiadiazole-4,7-diyl, 4-thien-2 -Yl-2,1,3-benzothiazol-7,5′-diyl, 4,7-dithien-2-yl-2,1,3-benzothiazole-5 ′, 5 ″ -diyl, imidazo [4 , 5-d] Imidazole-2,5-diyl, 4-alkyl-1,2,4-triazole-3,5-diyl, 9-alkylcarbazole-2,7-diyl, 6,12-dialkylindolo [ 2,3-b] carbazole-2 8-diyl, benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl, benzo [1,2-b: 5,4-b'] dithiophen-2,6-diyl, [1] benzothieno [3,2-b] [1] benzothiophen-2,7-diyl, benzo [1,2-d: 4,5-d ′] bisoxazole-2,6-diyl, benzo [1] , 2-d: 5,4-d '] bisoxazole-2,6-diyl, or 5,5-dioxodibenzothiophene-3,7-diyl diradical.

If hole transport properties are desired, indole and thiophene containing moieties such as those shown below may be preferred. * Represents a typical binding site.

  In the above structure, the R groups are selected as described for the E moiety.

If electron transport properties are desired, oxazole and oxadiazole containing moieties such as those shown below may be preferred. * Represents a typical binding site.

Such moieties provided as substituents that do not extend the chain length do not count against the limit of 1 to 20 aromatic / heteroaromatic moieties. That is, portions in the chain can be substituted with other aromatic or heteroaromatic rings. For example, depending on the location of the bond, each of the following structures will constitute a single part.

  In a preferred embodiment, the compound is a luminescent material and n is 1-6. In a further preferred embodiment, n is 3-6. In a preferred embodiment, n is 5-6. In a preferred embodiment, n is 5. In a further preferred embodiment, n is 6. Longer molecules are preferred because as the length of the aromatic core of the molecule increases, the energy efficiency of the device increases. Emission decay time measurements provide evidence that the increase in energy efficiency is due to triplet-triplet exciton annihilation that occurs in longer molecular cores, but is less likely to occur in shorter molecular cores. Further slight increases in energy efficiency can be achieved by further increasing the molecular core to n = 7 or 8, but the increased efficiency must be balanced with the increased cost of synthesizing such molecules. Must.

  A further preferred embodiment of the present invention is that the luminescent material of the present invention comprises a molecular core structure A terminated by an E unit. In charge transport or host material molecules, termination of the molecular core by multiple adjacent Ar units, such as phenyl-1,4-diyl, is due to strong intermolecular interactions mediated by π-π interactions between terminal Ar groups. It can be advantageous because the liquid crystal properties of the material can be enhanced and the charge carrier transport can be enhanced. However, in the case of luminescent materials, these same interactions can lead to quenching of the exciton energy, so that terminal E groups with a relatively bulky substituent at the 9-position are preferred.

Flexible linker groups S ¹ , S ^1a , S ² and S ^2a
If D represents a crosslinking group, the compounds of the present invention contain two flexible linker groups S ¹ and S ^2. As discussed herein, D can also represent more complex structures containing additional flexible linker groups S ^1a and S ^2a that are similar to the S ¹ and S ² groups. S ¹ , S ^1a , S ² , and S ^2a , in each ^occurrence, are independently selected from linear or branched C ₅ -C ₁₄ alkyl groups; 4, 4 or 5 methylene groups are replaced by oxygen atoms, provided that S does not contain a peroxide, ketal or acetal group, ie a valence or ether, ester, carbonate, thioether, amine or amide Attached to A through any of the bonds, i.e., as determined by the nature of D, either through a valence or an ether, ester, carbonate, thioether, amine or amide bond. , B ¹ , B ² , B ³ , or S ³ .

The flexible linker groups S ¹ , S ^1a , S ² and S ^2a function to separate the fluorescent system in A from the crosslinkable groups. When the material is cross-linked to the network polymer matrix, the flexible linker mechanically and electronically separates the phosphor from the polymer matrix. Thus, when the material is cross-linked to a polymer matrix, the flexible linker functions to reduce non-emissive exciton quenching, thereby promoting efficient luminescence.

D, B ¹ , B ² , and B ³
D, when representing indicating or ^{B 1} is hydrogen a crosslinkable group, D ^{is, -B 2 -S 3 -B 3 -S} 1a -A-S 2a -B 1a, -S 3 (B 2) ^{-B 3 -S 1a -A-S 2a} -B 1a, -S 3 (B 2) (B 3) -S 1a -A-S 2a -B 1a, -S 3 (B 2) (B 3), —A—S ² —B ¹ , or a crosslinkable group, wherein the dash at the left end of the chain represents the point of attachment to S ¹ . B ¹ , B ² , and B ³ each independently represent a crosslinkable group or hydrogen.

D is, when representing the ^-AS 2 -B ^1, D of A, ^{S 2,} and ^{B 1,} the remaining ^{D-S 1 -A-S 2} -B 1 structure A, ^{S 2,} and ^{B 1} and They may be the same or different. Preferably they are the same. That is, preferably, the compound is essentially a dimeric symmetric structure in which S ¹ forms a bond between half of the molecule. Provides an example of a dimeric ^{B 1 -S 2 A-S 1} -A-S 2 -B 1 structure below.

  We have found that these dimeric structures are synthetically simple approaches to increase molecular weight and thereby improve the film-forming properties of OLED materials due to increased viscosity. .

  Thus, the compounds of the present invention contain a crosslinkable group and form a network polymer when crosslinked. This is because the preferred crosslinkable groups react with two other crosslinkable groups resulting in a chain reaction and a polymer matrix.

  In a preferred embodiment, the crosslinkable group is selected from the group of ethylenic, diene, thiol and oxetane crosslinkable groups. An ethylene crosslinkable group is a crosslinkable group containing a carbon-carbon double bond. Diene crosslinkable groups can be considered as a subset of ethylenic crosslinkable groups. In a preferred embodiment, all crosslinkable groups independently represent an ethylene-based crosslinkable group. Preferred ethylenic crosslinkable groups include electron rich and electron deficient ethylenic crosslinkable groups.

  In a preferred embodiment, the crosslinkable group undergoes a crosslinking reaction upon radiation exposure. In a preferred embodiment, the crosslinkable groups undergo a crosslinking reaction upon exposure to ultraviolet (UV) light.

  Examples of preferred crosslinkable groups are linear and cyclic α, β-unsaturated esters, α, β-unsaturated amides, vinyl ethers, and non-conjugated diene crosslinkable groups. Accordingly, preferred crosslinkable groups include methacrylate, ethacrylate, ethyl maleate, ethyl fumarate, N-maleimide, vinyloxy, alkylvinyloxy, vinyl maleate, vinyl fumarate, N- (2-vinyloxymaleimide), and 1,4-pentadien-3-yl.

In a preferred embodiment, the crosslinkable group is an electron rich ethylenic crosslinkable group. Electron-rich ethylenic crosslinkable groups contain an ethylene group substituted with one or more electron donating groups. The electron donating group can include a heteroatom such as O, N, or S. In a preferred embodiment, the electron-rich crosslinkable group is a vinyloxy group. Other electron-donating group-substituted crosslinkable groups include p-alkoxystyrene, N-vinylpyrrolidone, N-vinylformamide, N-vinylalkylamide, and 1-alkenyl ethers such as propen-1-yloxy and butene-1-. Yloxy groups, cyclic vinyl ethers such as cyclohexen-1-yloxy and cyclopenten-1-yloxy, bicyclic vinyl ethers such as 2-norbornen-2-yloxy group, and vinyl ether groups are 4-vinyloxyphenyloxy and 2-vinyloxy Groups linked to a flexible linker or spacer (S ¹ , S ^1a , S ² , S ^2a , or S ³ ) via an intervening hydrocarbyl structure such as an ethyl group.

  In the above structure, n is independently 1-20 at each occurrence.

In a preferred embodiment, the crosslinkable group is an electron-deficient ethylenic crosslinkable group. An electron deficient ethylenic crosslinkable group contains an ethylene group substituted with one or more electron withdrawing groups. The electron withdrawing group can include a carbonyl group and can be, for example, an ester or an amide. In a preferred embodiment, the electron deficient crosslinkable group comprises a monoalkyl maleate group, a monoalkyl fumarate group, a monoaryl maleate group, a monoaryl fumarate group or a maleimide group. Other examples of electron-deficient crosslinkable groups include 4,4,4-trifluorocrotonate group, Z-4,4,4-trifluorobutenoate group, 3-trifluoromethyl-4,4,4-trifluoro group. With a fluorocrotonate group, Z- and E-3-cyanoacrylate, Z- and E-3-cyanomethacrylate, monoalkylcyclohexene-1,2-dicarboxylate, and monoalkylcyclopentene-1,2-dicarboxylate is there.

  In the above structure, n is independently 1-20 at each occurrence.

As described above, D is, or represents a crosslinkable group, or ^{if B 1} is hydrogen, D ^{is, -B 2 -S 3 -B 3 -S} 1a -A-S 2a -B 1a, -S ^{3 (B 2) -B 3 -S} 1a -A-S 2a -B 1a, -S 3 (B 2) (B 3) -S 1a -A-S 2a -B 1a or ^-S 3, ^{(B 2} ) (B ³ ), or a crosslinkable group, wherein the dash at the left end of the chain represents the point of attachment to S ¹ .

Accordingly, in one embodiment, D is of the structure ^{-B 2 -S 3 -B 3 -S 1a} -A-S 2a -B 1a, all elements of D are coupled linear. For purposes of illustration, in the example of this configuration, where the crosslinkable groups B ² and B ³ are fumarate groups and B ¹ and B ^1a represent hydrogen, the entire structure is a “type 1” S ³ spacer shown below. It is.

In a second embodiment, D is of the structure ^{-S 3 (B 2) -B 3} -S 1 -A-S 2a -B 1a, 1 single crosslinkable group ^{B 2} is branched from ^{S 3} Te to form a side chain which binds to S ^3. For purposes of illustration, the crosslinkable groups B ² and B ³ are fumarate groups, B ² terminates with a methyl group, and B ¹ and B ^1a represent hydrogen. In one example of this configuration, the entire structure is shown below. it is "type 2", which is the ^{S 3} spacer.

In a third aspect, D is the structure ^{S 3 (B 2) (B} 3) is of ^{-S 1 -A-S 2a -B 1a} , both ^{S 1} groups in the structure, the two crosslinking groups are bonded, cross-linked by a linker S ³ protruding. For purposes of illustration, in one example of this configuration, where the crosslinkable groups B ² and B ³ are monomethyl fumarate groups and B ^1a and B ¹ represent hydrogen, the entire structure is represented by the “type 3” S shown below. ³ spacers.

In a fourth aspect, D is is a structure ^{-S 3 (B 2) (B} 3). In this structure, the spacer group S ³ is decorated with two crosslinkable groups. For illustration, in one example of this arrangement, where the crosslinkable groups B ² and B ³ are monomethyl fumarate groups and B ¹ represents hydrogen, the entire structure is a “type 4” S ³ spacer shown below. is there.

S ³
D, when representing indicating or ^{B 1} is hydrogen a crosslinkable group, D ^{is, -B 2 -S 3 -B 3 -S} 1a -A-S 2a -B 1a, -S 3 (B 2) ^{-B 3 -S 1a -A-S 2a} -B 1a, -S 3 (B 2) (B 3) -S 1a -A-S 2a -B 1a or ^{-S 3, (B 2) (} B 3) Or a crosslinkable group, wherein the leftmost dash in the chain represents the point of attachment to S ¹ and B ^1a represents hydrogen. In this structure, there are additional spacer S ^3.

S ³ represents a non-chromogenic spacer group which can be rigid or flexible. S ³ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ haloalkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₆ -C ₁₆ aryl group, or a C ₄ -C ₁₅ heteroaryl group, or each independently And 1, 2, 3, 4 or 5 C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₃ -C ₈ cycloalkyl linked by a valence, ether or ester bond It may include a chain of the heteroaryl portion _{of the C} 6 _{-C 16} aryl, and / or _C 4 _{-C 15.} S ³ is linked to B ² and / or B ³ via a valence, ether, ester, or carbonate linkage.

Preferred examples of spacer ^{S 3} _is, C 2 _{-C 12} alkyl _group, C 3 -C ₈ cycloalkyl group, or _C 6 _{-C 16} aryl group, or each independently, Ataishirube, an ether bond or by an ester bond 1, 2, 3, 4 or 5 C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, and / or C ₄ attached comprising a chain consisting of heteroaryl portion of -C _15.

Examples of type 1 S ³ spacer group having B ² and B ³ crosslinkable groups are presented for clarity, are presented below (the wavy line indicates the point of attachment to the S ¹ and S ^1a).

In the above structure, n is independently in each occurrence 1 to 20, and m is 1 to 5.

Examples of type 2 S ³ spacer groups having B ² and B ³ crosslinkable groups are presented for clarity, are presented below (the wavy line indicates the point of attachment to another chain component).

Examples of type 3 S ³ spacer groups having B ² and B ³ crosslinkable groups are presented for clarity, are presented below (the wavy line indicates the point of attachment to another chain component):

Type 3 ^{S 3} spacer groups, these groups ^{B 1 -S 2 -A-S 1} -S 3 (B 2) (B 3) -S 1a -A-S 2a -B 1a structure for incorporation into whole It is particularly interesting because it is a chemical intermediate. Preferred examples of the type 3 ^{S 3} spacer _groups, C 2 _{-C 12} alkyl _group, C 3 -C ₈ cycloalkyl group, or _C 6 _{-C 16} aryl group, or each independently, Ataishirube, ether bond, or 1, 2, 3, 4, or 5 C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, and / or or comprising a chain consisting of _C 4 _{-C 15} heteroaryl moiety. In a preferred embodiment, the mold 3 ^{S 3} spacer _groups, C 2 _{-C 12} alkyl group, or _C 6 _{-C 16} aryl group, or each independently, Ataishirube, are linked by an ether bond, or ester bond, It comprises a chain consisting of 1, 2, 3, 4 or 5 C ₂ -C ₁₂ alkyl groups and / or C ₆ -C ₁₆ aryl groups. In a preferred embodiment, the mold 3 ^{S 3} spacer groups each independently, Ataishirube, are linked by an ether bond or an ester bond, 3, 4 or 5 amino _C 2 _{-C 12} alkyl group, and / or comprising a _C 6 _{-C 16} aryl group.

In a preferred embodiment, the mold 3 S 3 spacer groups each independently, Ataishirube, are linked by an ether bond or an ester bond, it is selected from C 2 -C 12 alkyl groups and C 6 -C 16 aryl group 5 groups. In type 3 S 3 spacer groups, crosslinking groups B 2 and B 3, C 3 ~C 12 alkyl group, is that it is bound to C 4 -C 10 alkyl group optionally this configuration, more excellent It is preferred because it provides improved structural flexibility and facilitates the resulting cross-linking reaction between B 2 and B 3 with the cross-linkable groups present in adjacent molecules. This gives the possibility of crosslinking under mild conditions, minimizing possible degradation.

Ｘ、Ｙ、およびＺは、独立して、価標、エーテル（Ｏ）、またはエステル結合（−ＣＯ_２）から選択され、ａ、ｂ、ｃ、ｄ、およびｅは、Ｃ_１〜Ｃ_２０結合（アルキル、ハロアルキル）を提供する整数である。 In a preferred embodiment, the mold 3 ^{S 3} spacer groups, Ataishirube, either by ether bond or an ester bond is bonded to _C 6 _{-C 16} aryl group of the central, four _C 2 _{-C 12} alkyl Group. In such a type 3 ^{S 3} spacer groups, the other end of the independent _C 2 _{-C 12} alkyl groups, respectively ^{B 2, B 3, S 1} , and bonded to terminate the ^{S 1a.} Examples of this preferred class of type 3 S ³ spacer groups are presented below. Wherein the wavy lines indicate points of attachment to other chain components and S ¹ and S ^1a , groups X, Y and Z independently represent a valence, ether or ester bond, a And d are in each case an integer from 2 to 12, and a and c in each case an integer from 1 to 11.

X, Y, and Z are independently selected from a valence, ether (O), or ester bond (—CO ₂ ), and a, b, c, d, and e are C ₁ -C ₂₀ bonds. Is an integer that provides (alkyl, haloalkyl).

Ｘ、Ｙ、およびＺは、独立して、価標、エーテル（Ｏ）、またはエステル結合（−ＣＯ_２）から選択され、ａ、ｂ、ｃ、ｄ、およびｅは、Ｃ_１〜Ｃ_２０結合（アルキル、ハロアルキル）を提供する整数である。 In a further preferred embodiment, the mold 3 ^{S 3} spacer groups, Ataishirube, either by ether bond or an ester bond are bonded to each other, three _C 2 _{-C 12} alkyl group, and two _C 6 ~ Includes C ₁₆ aryl groups. In such a structure, each C ₆ -C ₁₆ aryl group is: i) by a C ₂ -C ₁₂ alkyl group, to a second C ₆ -C ₁₆ aryl group, and ii) by a C ₂ -C ₁₂ alkyl group. the crosslinking agent ^{B 2} or ^{B 3,} iii) directly to ^{S 1} and ^{S 1a,} is coupled. Examples of this preferred class of type 3 S ³ spacer groups are presented below. Wherein the wavy lines indicate points of attachment to other chain components, S ¹ and S ^1a , groups X, Y and Z independently represent a valence, ether or ester bond, b And d are integers of 1 to 11, and a and c are integers of 1 to 10.

X, Y, and Z are independently selected from a valence, ether (O), or ester bond (—CO ₂ ), and a, b, c, d, and e are C ₁ -C ₂₀ bonds. Is an integer that provides (alkyl, haloalkyl).

Examples of structures incorporating the preferred type 3 S ³ spacer groups are presented below.

Examples of type 4 S ³ spacer groups having B ² and B ³ crosslinkable groups are presented for clarity, are presented below (the wavy line indicates the point of attachment to the S ^1).

  In the above structure, n and m in each occurrence are independently 1-20.

式中、Ｂ^１およびＢ^１ａは水素を表す。 Thus, in some cases, group D can be understood to be of the general structural type presented below.

In the formula, B ¹ and B ^1a represent hydrogen.

Further examples of structure D of the material of the present invention are provided below for illustration. Branches in the R group can be used to adjust the melting point of the material.

Material Properties The materials of the present invention are particularly useful for both their charge transport and emission properties. Accordingly, the materials described herein are useful in the manufacture of electronic devices such as organic light emitting diodes and photovoltaic devices.

  One advantageous property of the oligomer materials of the present invention is that they are soluble in common organic solvents. This is important because the solubility properties of the oligomers offer distinct advantages for device fabrication compared to, for example, polymeric materials. More specifically, these oligomeric materials can be used to fabricate devices by solution processing techniques. Briefly, this involves first dissolving the material, applying the solution to the substrate, and then evaporating to produce a film coating on the substrate. Once the material is deposited as a film, the material can be polymerized in situ. The polymerization can be initiated by exposure to radiation, such as ultraviolet light, which causes the crosslinkable groups of one molecule to crosslink with the crosslinkable groups of adjacent molecules to form a network polymer. Areas of the deposited film are masked from the starting radiation, providing areas of uncrosslinked material, while areas exposed to radiation undergo polymerization. The crosslinked material has negligible or low solubility compared to the solubility of the monomer, so that, if necessary, the unexposed non-crosslinked material can be washed away, leaving a patterned structure of the crosslinked material. Iterative cycles of solution deposition and polymerization can be used to produce structures with complex architectures.

  Sequentially deposited polymeric structures can be assembled in side-by-side or stacked / laminated fashion. In one example, sequential deposition and polymerization of red, green, and blue luminescent materials in a side-by-side fashion may be used to create pixels for a color display. In another example, a stack of red, green, and blue phosphor materials may be used to obtain a white light source. In another example, two or more emitter structures may be stacked to obtain a colored light source.

  The ability to inexpensively and economically produce multilayer devices in which adjacent layers have different highest occupied or lowest unoccupied molecular orbital (HOMO and LUMO) energy levels and different charge carrier mobilities is generally useful in plastic electronics. It is something. For example, using the materials and processes of the present invention, equivalent pn junctions can be formed, which can find utility in diodes, transistors, and photovoltaic devices. The tendency of the materials of the present invention to be patterned by photolithography makes it possible to produce a large number of plastic electronic devices of virtually any size and specification.

  The materials according to the invention can be mixed together to form a liquid crystal mixture. This can be very advantageous in terms of optimizing material properties for the intended application. For example, individual compounds of the present invention can have liquid crystals up to an isotropic liquid transition temperature that is much lower than their melting point (monomorphic liquid crystal phase). In device manufacturing applications, this results in a glassy or supercooled liquid film of material that is thermodynamically unstable enough to result in the risk of crystallization within the film and subsequent destruction of useful electronic properties. obtain. Mixing together multiple constituent compounds reduces the melting point of the resulting mixture to the isotropic liquid transition temperature under liquid crystal, or at least sufficiently suppresses crystallization, to eliminate this problem can do.

  Another advantage associated with using a mixture of the materials of the present invention is that even though they have certain properties that render them unusable as pure materials, materials that have otherwise very useful device application properties Can be used. For example, it may be desirable to prepare a luminescent liquid crystal film having a low liquid crystal transition temperature. The compounds of the present invention can be very efficient luminescent materials and can possess other useful properties, but can also be found to possess a high temperature liquid crystal phase. By dissolving the desired compound in a eutectic mixture of another compound of the invention having a lower temperature liquid crystal phase, a mixture having the required thermal properties can be obtained.

  A further advantage associated with using liquid crystal materials or mixtures of materials is that a directional or anisotropic structure can be formed. This directional order can be fixed in place, for example, by exposing the deposited film to radiation, such as ultraviolet light, by crosslinking the components of the deposited film.

  In a preferred example, the liquid crystal film can be deposited on a substrate that is coated with an alignment layer, such as a photo alignment layer. The components of the photo-alignment layer form a directional ordered structure upon exposure. This directional order in the alignment layer can then be transferred to a deposited liquid crystal film formed on its surface, and defined by polymerizing component oligomers by exposing the deposited ordered film to radiation, such as ultraviolet light. Resulting in a highly ordered device structure that can be fixed in position.

  Taking advantage of the possibility of obtaining a high device ordering device structure, it is possible to create a polarized light emitting structure in which the phosphor cores are oriented in the same direction and thus emit in the same direction. Ultimately, the properties of the materials described herein include the sequential deposition of uniformly oriented liquid crystal fluid or glass alignment layers, the sequential polymerization of the patterned areas of each layer in turn, and the non-polymerized areas of each layer in turn. Through sequential rinsing, the possibility of manufacturing a 3D display is provided, providing a light emitting structure such that the liquid crystal alignment and the polarization axis of the light emission of each layer are oriented in different directions.

  The materials of the present invention also have many additional desirable properties that make them useful for the production of electronic devices such as OLEDs. In organic light emitting devices, it is often desirable to reduce the self absorption of emitted light by the organic light emitting material. This self-absorption occurs because the spectral absorbance and emission band of the organic light emitting material more or less overlap in different materials. Solutions to this problem are well known, for example, in the field of dye lasers, where the luminescent material can be dissolved in a host that absorbs light at a shorter wavelength than the luminescent solute. When the solution is dilute, for example 1-2%, self-absorption of the luminescent solute is almost completely suppressed. The easy mutual miscibility of the various compounds of the present invention greatly facilitates the preparation of such solutions. Therefore, the material of the present invention is useful as a host material and a light emitting material.

  In organic light emitting device applications, there is a need for easy excitation energy transfer from the host material to the solute light emitting material. This is because charge carriers (electrons and holes) must be transported through the host medium to recombine to form excitons that emit light (electrically excited molecular orbital states). It is. In a mixture composed primarily of constituent host molecules, this recombination and exciton formation will occur primarily within the host molecule. The excitation energy then needs to be transferred from the host molecule to the luminescent solute molecule. The requirement for this energy transfer is that the spectral emission band of the host material overlaps the absorption band of the luminescent solute. Accordingly, an important aspect of the present invention is the preparation of mixtures of the compounds of the present invention having this spectral relationship between the constituent components. For example, a compound that emits light in the blue region of the spectrum can function as a host for a compound that is a green light emitter. Polymer films prepared by UV-induced cross-linking of a solution of a 5% green light-emitting compound in a blue light-emitting compound give significantly more green light emitted by the green light emitter than films prepared by UV cross-linking of the pure green light emitter. It will show less self-absorption.

  Yet another advantage of using a mixture of materials of the present invention is that reactive mesogenic materials in which photoinitiated electron donor / acceptor interactions are used to initiate polymerization, as opposed to ionic or free radical initiation. The use of a mixture of This can result in a much more stable (in terms of shelf life) reactive mesogenic material than in methacrylate-based systems, while at the same time maintaining low UV crosslinking fluence. In these mixtures, at least one of the reactive mesogenic materials is substituted with an electron-rich crosslinking group, while at least one other component reactive mesogenic material is substituted with an electron-deficient crosslinking group. I have. Ultraviolet radiation incident on the material promotes electron deficient crosslinkable groups on some reactive mesogen molecules to an electronically excited state. The excited, electron-deficient crosslinkable group then abstracts electrons from the electron-rich (electron donor) crosslinkable group on the other reactive mesogen molecule that initiates the copolymerization crosslinking reaction. The description of the photopolymerization in this mode is described in, for example, “Photoinitiated radical polymerization of vinyl ether-maleate systems”, Polymer 38, (9) pp. 2229-37 (1997), and "Co-Polymerization of Maleimides and Vinyl Ethers: A Structural Study", Macromolecules 1998, (31) pp. 5681-89.

  Electron deficient crosslinkable groups include maleimide, maleate, fumarate, and other unsaturated esters. Electron donating groups include vinyl ether, propenyl ether, and other similar alkenyl ethers. Mixtures such as these are advantageous in that the individual components are thermally and photochemically stable with good shelf life. However, once the materials are mixed, the mixture has high photochemical sensitivity and requires only a relatively small amount of UV for crosslinking.

Figures The present invention is described with reference to the following non-limiting figures. Further advantages of the present disclosure will become apparent by reference to the detailed description when considered in conjunction with the following drawings.

It is a graph which shows the UV / Vis absorption spectrum (blue) and PL spectrum (orange) in a solution about a non-crosslinkable compound. UV / Vis absorption in toluene has a concentration of 1 × 10 −5 M and PL has a concentration of 1 × 10 −6 M. All PL spectra were recorded at excitation = 350 nm, except for compounds K8-8 and L8-8 which were excited at 440 nm and 300 nm, respectively. The x-axis is the wavelength in nm and the y-axis is the absorbance on a normalized scale of 0-1. It is a graph which shows the UV / Vis absorption spectrum (blue) and PL spectrum (orange) in a solution regarding a crosslinking compound. UV / Vis absorption in toluene has a concentration of 1 × 10 −5 M and PL has a concentration of 1 × 10 −6 M. All PL spectra were recorded at excitation = 350 nm, except for compound K8-8MI, which was excited at 450 nm. It is a graph which shows a UV / Vis absorption spectrum (blue) and a PL spectrum (orange) about the thin film of a non-crosslinkable compound. All PL spectra were recorded at excitation = 350 nm, except for compounds K8-8 and L8-8 which were excited at 450 nm and 300 nm, respectively. It is a graph which shows a UV / Vis absorption spectrum (blue) and a PL spectrum (orange) about the thin film of a crosslinking compound. All PL spectra were recorded at excitation = 350 nm, except for compounds K8-8 and L8-8 which were excited at 450 nm and 300 nm, respectively. Figure 4 is a graph showing sensitivity plots for two biphenyldibenzo [d, b] silole crosslinkable donor-acceptor mixtures. Fumarate / vinyl ether 1: 1 (gray) and methacrylate / vinyl ether 1: 1 (yellow) are shown. The x-axis is the exposure in J / cm ² and the y-axis is the percent crosslinking achieved, ie, the conversion of monomeric species to crosslinked polymer species.

式中、Ｘ＝Ｓｉである。 Biphenyldibenzo [d, b] silole:

Where X = Si.

ＭｃＤｏｗｅｌｌ ｅｔ ａｌ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２０１３，４６，６７９４−６８０５からの合成。

Synthetic Examples The compounds of the present invention can be synthesized by common techniques in organic synthesis well known to those skilled in the art. Examples are given below on how these compounds can be synthesized. As can be appreciated, the nature of these materials allows a modular approach to synthesis to be employed, and the silafluorene core can be integrated into a range of materials by standard chemical techniques. In this way, the properties of all constituents of the material, such as core A, various flexible linker / spacer groups (S ¹ , S ^1a , S ² , S ^2a , and S ³ ) and various crosslinkers and crosslinks The agent-containing structures (D, B ¹ , B ² , and B ³ ) can be easily adjusted to fine tune bulk material properties such as melting point, liquid crystal properties, and luminescent properties. The examples presented below are by way of example only and in no way limit the scope of the invention.
Synthesis from Jin et al, Macromolecules, 2011, 44, 502-511

Synthesis from McDowell et al, Macromolecules, 2013, 46, 6794-6805.

Synthesis of 4,4'-dibromo-3,3'-dimethoxy-1,1'-biphenyl: o-dianisidine (10.0 g, 40 mmol) was charged to 40 in a 1 L three-neck flask equipped with a thermometer and a dropping funnel. % HBr aqueous solution ₍₄₀ mL), was mixed with H 2 O (160mL), and acetonitrile (160 mL). After the starting materials had dissolved in acetonitrile, the reaction mixture was cooled to 0 ° C. in an ice bath. A cooled solution of sodium nitrate (7.2 g, 104.4 mmol) in H ₂ O (14 mL) was added dropwise to the reaction mixture so that the temperature did not exceed 10 ° C. After the addition, the reaction mixture was stirred at 0 ° C. for 30 minutes. Thereafter, freshly prepared CuBr (13.0 g, 90.6 mmol) in a 40% aqueous HBr solution (160 mL) was added slowly via cannula, ensuring that the temperature of the reaction mixture did not exceed 10 ° C. (in order to avoid side reactions of O ₂ in the atmosphere). After the addition, the reaction mixture was warmed to room temperature and then heated to reflux for 1 hour. The solution was then cooled to room temperature and extracted with CHCl ₃ (3 × 100 mL). The combined organic extracts were then washed with 10% aq. NaOH and brine, finally dried (MgSO ₄ ), filtered and evaporated to dryness under reduced pressure. The crude product was used for next step without further purification.

Synthesis of 4,4'-dibromo-2,2'-diiodo-5,5'-dimethoxy-1,1'-biphenyl: 4,4'-dibromo-3,3'-dimethoxy-1,1'-biphenyl _{(13.0g, 34.9mmol), KIO 3} (3.3g, 15.4mmol), and _I 2 (9.6g, _38.0mmol) and acetic acid (260 mL) and 7.5MH ₂ SO ₄ (26mL) Was dissolved in the mixture. The solution was heated at 80 ° C. for 12 hours. Upon completion, the reaction mixture was cooled to room temperature _and diluted with H 2 O (250mL). The precipitate was collected by filtration, dried under vacuum and dissolved in a minimum amount of CHCl ₃ (200 mL). The organic solution was washed with 10% aqueous NaOH and brine, then dried (MgSO ₄ ), filtered and evaporated to dryness under reduced pressure. The crude product was then purified by recrystallization from boiling ethanol to give the product as brown needles.

Synthesis of 2,7-dibromo-3,6-dimethoxy-9,9-dihexylsilafluorene: 4,4′-dibromo-2,2′-diiodo-5,5′-dimethoxy-1,1′-biphenyl ( (4.0 g, 6.41 mmol) was dissolved in dry THF (60 mL) in a Schlenk flask under Ar and stirred vigorously. The reaction mixture was cooled to −110 ° C. in a MeOH / N ₂ bath and then n-BuLi (8.07 mL, 12.9 mmol, 1.6 M in hexane) was added dropwise over 30 minutes. The reaction mixture was then stirred at -110 C for a further 30 minutes. Next, di-n-hexyldichlorosilane (1.96 mL, 7.1 mmol) was added and the reaction mixture was warmed to room temperature and stirred for another 10 hours. The reaction mixture was then quenched by the addition of water and the product was extracted with diethyl ether. The combined organics were washed with brine, dried (MgSO _4), filtered, then the solvent was removed under reduced pressure. The product was then purified by recrystallization from boiling ethanol.

Schemes and synthetic preparation of silafluorene compounds A and B

4,4'-Dibromo-2,2'-diiodo-1,1'-biphenyl t-BuLi (15.3 ml, 0.0261 mol, 1.7 M in pentane) was added to 4,4'-dibromo-2,2. To a solution of '-diiodobiphenyl (3.50 g, 6.21 mmol) in dry THF (40 ml) was added slowly over 30 minutes at -95 ° C (hexane / liquid nitrogen) under a nitrogen inert atmosphere. The reaction mixture was stirred at −95 ° C. for another hour, followed by addition of dichlorohexylsilane (3.34 g, 0.0124 mol) and stirring at room temperature overnight. Water (50 ml) was added and the product was extracted into diethyl ether (3 × 50 ml), the ether extract was washed with water (150 ml), dried (MgSO ₄ ), filtered and concentrated under reduced pressure. . The crude product was purified by gravity column chromatography (wet packing, silica gel, hexane) to give a colorless oil (1.67 g, 53%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.68 (2H, d, J = 2.0 Hz), 7.63 (2H, d, J = 8.4 Hz), 7.54 (2H) , Dd, J = 2.0 and 8.0 Hz), 1.19-1.33 (16H, m), 0.91-0.95 (4H, m), 0.84 (6H, t).

2,7-bis (4-octyloxybiphenyl-4'-yl) -9,9-dihexylsilafluorene [Compound C]
4-octyloxybiphenyl-4′-yl-boronic acid (2.36 g, 7.24 mmol), 2,7-dibromo-9,9-dihexylsilafluorene (Compound A, 1.60 g, 3.15 mmol), K ₂ CO ₃ (2.17 g, 15.7 mmol), toluene (30 ml) and water (15 ml) were all added to the three neck round bottom flask and the system was evacuated using a vacuum pump and filled with nitrogen three times. . Subsequently, Pd (PPh ₃ ) ₄ (0.36 g, 0.31 mmol) was added and the reaction mixture was stirred under reflux overnight. The reaction mixture was poured into a separatory funnel, to which both water (30 ml) and toluene (30 ml) were added, the aqueous layer was washed with toluene (15 ml), the combined organic layer was washed with water (50 ml), Dried (MgSO ₄ ) and filtered. The crude product was purified by gravity column chromatography (silica gel, 30% DCM in hexane) to give a white powder (2.00 g, 69.7%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.82-7.95 (4H, m), 7.61-7.76 (10H, m), 7.58 (4H, d, J) = 8.8 Hz), 6.99 (4H, d, J = 8.8 Hz), 4.01 (4H, t), 1.82 (4H, quint), 1.20-1.53 (36H, m ), 1.00-1.04 (4H, m), 0.91 (6H, t), 0.83 (6H, t). MALDI-MS: 910.5 (M ^<+> ).

2,7-bis (4-octyloxybiphenyl-4'-yl) -9,9-dioctylsilafluorene [Compound D]
4-octyloxybiphenyl-4′-yl-boronic acid (0.77 g, 2.36 mmol), 2,7-dibromo-9,9-dioctylsilafluorene (Compound B, 0.58 g, 1.03 mmol), K ₂ CO ₃ (0.71 g, 5.14 mmol), toluene (10 ml), and water (5 ml) were all added to the three neck round bottom flask, and the system was evacuated using a vacuum pump and filled with nitrogen three times. did. Subsequently, Pd (PPh ₃ ) ₄ (0.12 g, 0.103 mmol) was added and the reaction mixture was stirred under reflux overnight. The reaction mixture was poured into a separatory funnel, to which both water (25 ml) and toluene (25 ml) were added, the aqueous layer was washed with toluene (10 ml), the combined organic layer was washed with water (50 ml), Dried (MgSO ₄ ) and filtered. The crude product was purified by gravity column chromatography (silica gel, 30% DCM in hexane) to give a white solid (0.40 g, 40.4%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.89-7.92 (4H, m), 7.63-7.73 (10H, m), 7.59 (4H, d, J) = 8.8 Hz), 7.00 (4H, d, J = 8.8 Hz), 4.02 (4H, t), 1.82 (4H, quint), 1.20-1.53 (44H, m ), 1.00-1.04 (4H, m), 0.90 (6H, t), 0.83 (6H, t). MALDI-MS: 966.6 (M ^<+> ).

Dibenzo [d, b] silole (silafluorene) -based photocrosslinkable liquid crystals: synthesis, optical properties and liquid crystal action The following examples illustrate n-alkyl-5H-dibenzo [b, d] silole-based for OLED applications. With respect to the synthesis and characterization of liquid crystal materials, it has the added advantages of ease of synthesis, a broader liquid crystal phase transition temperature range (ie, from the liquid crystal state to the isotropic liquid state), and improved photocrosslinking efficiency. Throughout the examples, a comparison is made between n-alkyl-5H-dibenzo [b, d] silole-based materials and similar n-alkylfluorene-based materials.

架橋性：

Examples of the invention relate to the following structures, both crosslinkable and non-crosslinkable structures:
Non-crosslinkable:

Crosslinkability:

Synthesis and Characterization A total of 10 variants of the material containing the dibenzo [d, b] silole core structure were the major commercially available intermediate 9,9-dioctyl-9H-9-silafluorene-2,7-bis ( (Boronic acid) synthesized from pinacol ester (compound 5).

  The boronic acid pinacol ester is used in various Suzuki couplings with the corresponding aryl bromide to provide any of the desired bisphenol intermediates (compounds 6 and 14) or a final product such as L8-8. Supplied directly. Using different choices of Williamson-ether synthesis conditions, the bis-phenol can be coupled to various alkyl bromides to give the desired crosslinkable end products (J8-8VE, J8-8MI, and K8-8MI). Or providing the bis-phenoxy-octan-1-ol derivative (Compound 13) used to synthesize the other end products (J8-8MET, J8-8FUM, and J8-8MAL). It was possible. When designing the material, five different crosslinkable groups, such as vinyl ether (electron rich), and four electron deficient groups, such as methacrylate, fumarate, maleate, and maleimide, were selected for bonding around the molecule. Since they were all attached to the biphenyl-substituted dibenzo [d, b] silole core via equivalent spacers, the photocrosslinking properties of this new family of materials could be evaluated. In addition to these photocrosslinkable compounds, non-crosslinkable analogs were synthesized for comparison. Chemical synthesis is designed to be as simple as possible to keep costs low and increase the potential for scale-up, which makes the material more commercially viable.

  Both non-crosslinkable (K8-8) and crosslinkable (K8-8MI) compounds containing a phenyl-benzothiadiazole group attached to a central dibenzo [d, b] silole core were synthesized. The phenyl-benzothiadiazole unit was chosen to shift the emission red to the green region of the visible spectrum. Both crosslinkable and non-crosslinkable versions were synthesized so that the effect of adding a crosslinkable group to the luminescent core could be evaluated. The maleimide group was chosen as a crosslinkable moiety for the green emitting compound due to the very efficient photocrosslinking results observed with the blue emitting biphenyl version.

  A dulen-phenyl substituted compound (L8-8) was synthesized as a potential host for the blue emitting dopant J8-8. It was hypothesized that replacing one of the phenyl rings in the biphenyl unit with a dulen unit could reduce the effective conjugation of the molecule. The dulen unit should be able to twist and increase the dihedral angle between the dibenzo [d, b] silole central core and the dulen-phenyl aromatic group, which increases the band gap of the material and potentially more Compounds can be provided that can be used as host materials for small bandgap emissive dopant materials.

The compounds of the present invention can be synthesized by common techniques in organic synthesis that are well known to those skilled in the art. Examples are given below on how these compounds can be synthesized. As can be appreciated, the nature of these materials allows a modular approach to be employed in chemical synthesis. In this way, the material properties of all components of (Formula ^{D-S 1 -A-S 2} -B 1, 14 see patent family), for example core A, a variety of flexible linker / spacer group ( S ¹ , S ^1a , S ² , S ^2a , and S ³ ) and various crosslinkers and crosslinker-containing structures (D, B ¹ , B ² , and B ³ ) have melting point, liquid crystal, and luminescent properties. Can be easily adjusted to fine tune the properties of the bulk material. The materials shown below are merely examples and do not limit the scope of the invention in any way.

スキーム１。５，５−ジアルキル−５Ｈ−ジベンゾ［ｂ，ｄ］シロール−３，７−ビフェニル誘導体Ｊ６−８およびＪ８−８の合成。 Scheme 1
3,7-Dibromo-5,5-dihexyl-5H-dibenzo [b, d] silole (2) is combined with t-BuLi to form 4,4′-dibromo-2,2′-diiodobiphenyl (1). The workup synthesized in good yield (53%) to form the lithium salt, followed by quenching with dichlorohexylsilane. Compound 3 was purchased commercially and Suzuki coupling reaction of both compounds (2) and (3) with boronic acid (4) provided the final materials J6-8 and J8-8.

Scheme 1. Synthesis of 5,5-dialkyl-5H-dibenzo [b, d] silole-3,7-biphenyl derivatives J6-8 and J8-8.

3,7-dibromo-5,5-dihexyl-5H-dibenzo [b, d] silole (2)
t-BuLi (15.3 mL, 0.0261 mol, 1.7 M in pentane) was added to 4,4′-dibromo-2,2′-diiodobiphenyl (Compound 1, 3.50 g, 6.21 mmol) in dry THF. (40 mL) was added slowly to the solution at -95 <0> C (hexane / liquid nitrogen) over 30 minutes under a nitrogen inert atmosphere. The reaction mixture was stirred at −95 ° C. for an additional hour, followed by addition of dichlorohexylsilane (3.34 g, 0.0124 mol) and stirring at room temperature overnight. Water (50 mL) was added, the product was extracted into diethyl ether (3 × 50 mL), and the ether extract was washed with water (150 mL), dried (MgSO ₄ ), filtered and concentrated under reduced pressure. . The crude product was purified by gravity column chromatography (wet packing, silica gel, hexane) to give compound 2 as a colorless oil (1.67 g, 53%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.84 (6H, t, J = 6.8 Hz, CH ₃ ), 0.91-0.95 (4H, m, CH ₂ ); _{18-1.33 (16H, m, CH 2} ), 7.53 (2H, dd, J = 2.0 and 8.0Hz, Ar-H), 7.63 (2H, d, J = 8.4Hz , Ar-H), 7.68 (2H, d, J = 2.0 Hz, Ar-H).

3,7-bis (4-octyloxybiphenyl-4'-yl) -5,5-dihexyl-5H-dibenzo [b, d] silole (J6-8)
4-octyloxybiphenyl-4′-boronic acid (compound 4, 2.36 g, 7.24 mmol), 3,7-dibromo-5,5-dihexyl-5H-dibenzo [b, d] silole (compounds 2, 1 .60 g, 3.15 mmol), K ₂ CO ₃ (2.17 g, 15.7 mmol), toluene (30 ml), and water (15 ml) were all added to a three neck round bottom flask and using nitrogen as inert gas. The system was degassed using two freeze-pump-thaw cycles. _{Subsequently,} the addition of _{Pd (PPh 3) 4 (0.36g} , 0.31mmol), the reaction mixture, one freeze - was degassed again by thaw cycles - pump. The reaction mixture was stirred at 90 ° C. for 18 hours, poured into a separatory funnel, whereupon both water (30 ml) and toluene (30 ml) were added, the aqueous layer was washed with toluene (15 ml), and the combined organic layers were washed. Washed with water (50 ml), dried (MgSO ₄ ) and filtered. The crude product was purified by gravity column chromatography (dry packing, silica gel, 20% dichloromethane in hexane) to give compound J6-8 as a white powder (2.00 g, 69.7%). Further purification can be performed by recrystallization from the DCM / ethanol layer.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.83 (6H, t, J = 6.8 Hz, CH ₃ ), 0.90 (6H, t, J = 7.0 Hz, CH ₃ ), _{1.00-1.04 (4H, m, CH 2} ), 1.19-1.51 (36H, m, CH 2), 1.82 (4H, quint., CH 2), 4.02 (4H , T, J = 6.6 Hz, CH ₂ ), 7.00 (4H, d, J = 8.8 Hz, Ar-H), 7.59 (4H, d, J = 8.8 Hz, Ar-H) , 7.66 (4H, d, J = 8.8 Hz, Ar-H), 7.72 (6H, d, J = 8.0 Hz, Ar-H), 7.88 (2H, d, J = 2) 0.0 Hz, Ar-H), 7.92 (2H, d, J = 8.0 Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (CH ₃ ), 14.3 (CH ₃ ), 22.7 (CH ₂ ), 22.8 ( _{CH 2), 24.1 (CH 2} ), 26.2 (CH 2), 29.4 (CH 2), 29.5 (x2) (CH 2), 31.5 (CH 2), 32.0 _{(CH 2), 33.3 (CH} 2), 68.3 (CH 2), 115.0 (CH), 121.4 (CH), 127.2 (CH), 127.5 (CH), 128 .1 (CH), 129.0 (CH), 131.9 (CH), 133.2 (C), 139.0 (C), 139.5 (C), 139.6 (C), 139. 9 (C), 147.4 (C), 159.0 (CO). MALDI-MS: 910.6 (M ^<+> ). Elemental analysis: expected value C = 84.34, H = 9.07, measured value C = 84.32, H = 9.00.

3,7-bis (4-octyloxybiphenyl-4'-yl) -5,5-dioctyl-5H-dibenzo [b, d] silole (J8-8)
4-octyloxybiphenyl-4′yl-boronic acid (compound 4, 0.77 g, 2.36 mmol), 3,7-dibromo-5,5-dioctyl-5H-dibenzo [b, d] silole (compound 3, 0.58 g, 1.03 mmol), K ₂ CO ₃ (0.71 g, 5.14 mmol), toluene (10 ml), and water (5 ml) were all added to a three-necked round bottom flask, and nitrogen was added as an inert gas. Used, the system was degassed using two freeze-pump-thaw cycles. _{Subsequently,} the addition of _{Pd (PPh 3) 4 (0.12g} , 0.103mmol), the reaction mixture, one freeze - was degassed again by thaw cycles - pump. The reaction mixture was stirred at 90 ° C. for 18 hours, poured into a separatory funnel, further added with both water (25 ml) and toluene (25 ml), the aqueous layer was washed with toluene (10 ml), and the mixed organic layer was washed. Washed with water (50 ml), dried (MgSO ₄ ) and filtered. The crude product was purified by gravity column chromatography (dry packing, silica gel, 20% dichloromethane in hexane) to give compound J8-8 as a white powder (0.40 g, 40.4%). Further purification can be performed by recrystallization from the DCM / ethanol layer.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.83 (6H, t, J = 6.8 Hz, CH ₃ ), 0.90 (6H, t, J = 6.8 Hz, CH ₃ ), _{1.00-1.04 (4H, m, CH 2} ), 1.20-1.51 (44H, m, CH 2), 1.82 (4H, quint., CH 2), 4.02 (4H , T, J = 6.6 Hz, CH ₂ ), 7.00 (4H, d, J = 8.8 Hz, Ar-H), 7.59 (4H, d, J = 8.8 Hz, Ar-H) , 7.65 (4H, d, J = 8.4 Hz, Ar-H), 7.72 (6H, d, J = 8.4 Hz, Ar-H), 7.88 (2H, d, J = 1) .6 Hz, Ar-H), 7.92 (2H, d, J = 8.0 Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (CH ₃ ), 14.3 (CH ₃ ), 22.8 (x2) (CH ₂ ), 24 2 (CH ₂ ), 26.2 (CH ₂ ), 29.3 (CH ₂ ), 29.4 (x2) (CH ₂ ), 29.5 (x2) (CH ₂ ), 32.0 (CH ₂ ), 33.6 (CH ₂ ), 68.3 (CH ₂ ), 115.0 (CH), 121.4 (CH), 127.2 (CH), 127.5 (CH), 128.1 (CH), 129.0 (CH), 131.9 (CH), 133.2 (C), 139.0 (C), 139.5 (C), 139.6 (C), 139.8 ( C), 147.3 (C), 159.0 (CO). MALDI-MS: 966.6 (M ^<+> ). Elemental analysis: Expected C = 84.41, H = 9.38, found C = 84.47, H = 9.29.

スキーム２。誘導体Ｊ８−８ＶＥおよびＪ８−８ＭＩの合成。 Scheme 2
First, dioxane _{/ H 2 O (3: 1} ) catalyst Pd Suzuki coupling between _{(PPh 3) 4} Commercially available boronic acid ester with a (5) and 4-bromo-4'-hydroxybiphenyl in The reaction provided bis-phenol (6) in good yield (66%). Due to the low solubility of compound (6) in moderately polar solvents, purification was performed simply by washing with dichloromethane and filtering. The bromo-alkyl Diels-Alderfuran-maleimide adduct (10) was reacted with (6) by the Williamson-ether reaction in DMF at 50 ° C. to give a medium yield (31%) of J8-8MI. A protected derivative of was obtained. Subsequent deprotection by heating in toluene provided the final maleimide material J8-8MI in moderate yield (44%). Compound J8-8VE was synthesized in good yield (51%) by a Williamson-ether reaction using potassium carbonate as the base in refluxing butanone.

Scheme 2. Synthesis of derivatives J8-8VE and J8-8MI.

3,7-bis (4-hydroxybiphenyl-4'-yl) -5,5-dioctyl-5H-dibenzo [b, d] silole (6)
4-bromo-4'-hydroxybiphenyl (3.40 g, 13.7 mmol), 5,5-dioctyl-3,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) -5H- dibenzo [b, d] silole (compound _{5,3.00g, 4.55mmol), Na 2 CO} 3 (18.0g), DME (180mL), and water (90 mL) all three neck Added to round bottom flask. The system was degassed using sonication under vacuum (30 seconds) and then backfilled with nitrogen and the process was repeated 10 times. Subsequently, Pd (PPh ₃ ) ₄ (0.53 g, 0.45 mmol) was added and the reaction mixture was stirred at reflux under nitrogen for 18 hours. The reaction mixture was then acidified with 10% HCl (200 mL), then poured into a separatory funnel, the aqueous layer was extracted with ethyl acetate (3 × 150 mL), and the combined organics were washed with water (200 mL) and dried ( MgSO ₄ ) and filtered. After filtration, the organic layer was evaporated to dryness under reduced pressure and the crude product was purified by trituration under dichloromethane (50 mL) and washed repeatedly with dichloromethane (2 × 100 mL) to give a white powder (3. Compound 6 (00 g, 88.8%).
¹ H NMR (400 MHz, CO (CD ₃ ) ₂ ): δ (ppm) 0.78 (6 H, t, J = 7.0 Hz, CH ₃ ), 1.07-1.30 (24 H, m, CH _{2 ), 1.41-1.49 (4H, m,} CH 2), 6.93-6.97 (4H, m, Ar-H), 7.53-7.57 (4H, m, Ar-H ), 7.60 (2H, dd, J = 8.1, 2.0 Hz, Ar-H), 7.63-7.66 (4H, m, Ar-H), 7.71-7.76 ( 6H, m, Ar-H), 8.11 (2H, d, J = 1.9 Hz, Ar-H), 8.51 (2H, s, OH). MALDI-MS: 742.3 (M ^<+> ).

3,6-endo, exo-oxo-Δ ⁴ -tetrahydrophthalimide (8)
A solution of maleimide (7, 2.50 g, 25.8 mmol) and furan (10 mL) in ethyl acetate (20 mL) was stirred at room temperature for 3 days. The resulting precipitate was filtered and dried under vacuum to give a white powder (3.00 g, 71%). Product 8 was obtained as a mixture of endo- and exo-adducts (1.6: 1).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) End product: 3.6 (s, 2H), 5.35 (s, 2H), 6.6 (s, 2H), exo product: 2 .9 (s, 2H), 5.35 (s, 2H), 6.6 (s, 2H).

8- (3,6-exo-oxo-Δ ⁴ -tetrahydrophthalimide) bromooctane (10)
Compound 8 (0.76g, 4.6mmol), 1,8- dibromo-octane (9,5.0g, 18.4mmol), and _{K 2 CO 3 (3.18g, 23.0mmol} ) the mixture of dry DMF (10 mL) and stirred at 55 ° C. under a nitrogen atmosphere for 18 hours. DMF was removed under reduced pressure, the residue was redissolved in dichloromethane (50 mL) and the salts were removed by filtration. The filtrate is evaporated to dryness under reduced pressure and the crude product is purified by column chromatography (silica gel, 30% ethyl acetate in hexane to 50% ethyl acetate in hexane) to give the compound as a viscous liquid crystallized overnight. 10 (0.40 g, 24%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) exo product: 1.20-1.60 (m, 10H), 1.85 (quint., 2H), 2.9 (s, 2H), 3.40 (trip., 2H), 3.50 (trip., 2H), 5.35 (s, 2H), 6.6 (s, 2H).

J8-8MI
Compound 6 (1.00 g, 1.35 mmol), compound 10 (1.44 g, 4.04 mmol), and _{K 2 CO 3 (0.93g, 6.73mmol} ) and the mixture of suspended in dry DMF (50 mL) It became cloudy. The reaction mixture was heated to 55 ° C. and stirred under nitrogen for 20 hours. Upon completion, the reaction mixture was cooled to room temperature and the salts were removed by filtration. The filtrate was evaporated under reduced pressure. The residue was redissolved in dichloromethane (100 mL) and washed with water (3 × 100 mL). The organic layer was dried (MgSO _4), filtered and evaporated to dryness under reduced pressure. The crude product was then purified by flash column chromatography (50% ethyl acetate in hexane to 100% ethyl acetate) to give the protected maleimide derivative as a yellow solid (0.54 g, 31%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.84 (6H, t, J = 7.0 Hz, CH ₃ ), 1.01 to 1.05 (4H, m, CH ₂ ), 1. _{21-1.62 (44H, m, CH 2} ), 1.78-1.85 (4H, m, CH 2), 2.84 (4H, s, CH), 3.49 (4H, t, J _{= 7.3Hz, CH 2), 4.01} (4H, t, J = 7.5Hz, CH 2), 5.28 (4H, s, CH), 6.52 (4H, s, = CH), 7.00 (4H, br d, J = 8.7 Hz, Ar-H), 7.59 (4H, br d, J = 8.7 Hz, Ar-H), 7.66 (4H, br d, J) = 8.2 Hz, Ar-H), 7.72-7.74 (6H, m, Ar-H), 7.90 (2H, d, J = 1.5 Hz, Ar-H), 7.93 ( H, d, J = 8.2Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.4 (CH ₂ ), 14.1 (CH ₃ ), 22.6 (CH ₂ ), 24.0 (CH ₂ ), 25.9 ( _{CH 2), 26.6 (CH 2} ), 27.5 (CH 2), 29.0 (CH 2), 29.1 (CH 2), 29.2 (3x) (CH 2), 31.8 _{(CH 2), 33.4 (CH} 2), 39.0 (CH 2), 47.4 (CH), 68.1 (CH 2), 80.9 (CH), 114.9 (CH), 121.2 (CH), 127.0 (CH), 127.3 (CH), 128.0 (CH), 128.9 (CH), 131.7 (CH), 133.0 (C), 136 .5 (CH), 138.8 (C), 139.4 (C), 139.5 (C), 139.7 (C), 147.2 (C), 158.8 (C), 176.3 (C = O). MALDI-MS: 1293.7 (MH ^<+> ).

The protected maleimide (0.53 g, 0.41 mmol) was heated at reflux in toluene (10 mL) for 16 hours to completely remove the furan. The toluene was removed under reduced pressure and the crude product was purified by flash chromatography (100% dichloromethane to 2% ethyl acetate in dichloromethane) to give an off-white waxy solid. This was further purified by trituration in ethanol to give J8-8MI as an off-white solid (0.21 g, 44%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.84 (6H, t, J = 7.0 Hz, CH ₃ ), 1.01 to 1.05 (4H, m, CH ₂ ), 1. _{21-1.52 (40H, m, CH 2} ), 1.57-1.65 (4H, m, CH 2), 1.78-1.85 (4H, m, CH 2), 3.53 ( _{4H, t, J = 7.3Hz,} CH 2), 4.02 (4H, t, J = 6.5Hz, CH 2), 6.70 (4H, s, CH = CH), 6.99-7 .02 (4H, m, Ar-H), 7.57-7.61 (4H, m, Ar-H), 7.65-7.68 (4H, m, Ar-H), 7.71- 7.74 (6H, m, Ar-H), 7.90 (2H, d, J = 1.8 Hz, Ar-H), 7.93 (2H, d, J = 8.1 Hz, Ar-H) . ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.4 (CH ₂ ), 14.1 (CH ₃ ), 22.6 (CH ₂ ), 24.0 (CH ₂ ), 26.0 ( CH ₂ ), 26.7 (CH ₂ ), 28.5 (CH ₂ ), 29.0 (CH ₂ ), 29.1 (CH ₂ ), 29.2 (3x) (CH ₂ ), 31.8 _{(CH 2), 33.4 (CH} 2), 37.9 (CH 2), 68.0 (CH 2), 114.9 (CH), 121.2 (CH), 127.0 (CH), 127.3 (CH), 128.0 (CH), 128.9 (CH), 131.7 (CH), 133.0 (C), 134.0 (CH), 138.8 (C), 139 .4 (C), 139.5 (C), 139.7 (C), 147.2 (C), 158.8 (C), 170.9 (C = O ). MALDI-MS: 1156.6 (M ^<+> ). Elemental analysis: Expected C = 78.85, H = 8.01, N = 2.42, found C = 78.75, H = 7.93, N = 2.45.

8-bromo-1-vinyloxyoctane (compound 12)
The three-necked round bottom flask equipped with a water cooler was vacuum dried using a heat gun. After cooling to room temperature, 8-bromo-1-octanol (11, 15.0 g, 0.0717 mol), vinyl acetate (dried using K ₂ CO ₃ , distilled, 12.4 g, 0.1435 mol), Na ₂ CO ₃ (dried at 80 ° C. under vacuum for 5 hours, 4.65 g, 0.0430 mol) and toluene (dry and degassed, 150 mL) were added, and the atmosphere was replaced with nitrogen. The catalyst [Ir (cod) Cl] ₂ (0.96 g, 0.0014 mol) was added and the reaction mixture was stirred at 100 ° C. for 2 hours. The reaction mixture was cooled to room temperature and the toluene was removed under reduced pressure. The crude product was purified by a short silica gel plug (wet-packed, 20% dichloromethane in hexane) followed by flash column chromatography (wet-packed, 3% diethyl ether in hexane) to give a yellow oil (4.45 g, Compound 2 was obtained as 26.3%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 1.30-1.45 (m, 8H), 1.65 (quint., 2H), 1.85 (quint., 2H), 3.40 (T, 2H), 3.67 (t, 2H), 3.97 (dd, 1H), 4.16 (dd, 1H), 6.46 (dd, 1H).

J8-8VE
A solution of compound 6 (0.50 g, 0.67 mmol) and compound 12 (0.47 g, 2.02 mmol) containing Cs ₂ CO ₃ (1.10 g, 3.36 mmol) in butanone (20 mL) was degassed, and nitrogen was added. The mixture was stirred under reflux for 20 hours. After completion, the salts were removed by filtration and the filtrate was evaporated to dryness under reduced pressure. The crude product was then redissolved in dichloromethane (50 mL) and washed with water (2 × 50 mL). The organic layer was then dried (MgSO _4), filtered, and concentrated under reduced pressure. The crude product was then purified by trituration in ethanol and recrystallized from a DCM / ethanol layer to give a white solid (0.36 g, 51%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.84 (6H, t, J = 7.0 Hz, CH ₃ ), 1.01 to 1.05 (4H, m, CH ₂ ), 1. _{21-1.30 (20H, m, CH 2} ), 1.40-1.52 (20H, m, CH 2), 1.65-1.70 (4H, m, CH 2), 1.80- _{1.87 (4H, m, CH 2} ), 3.70 (4H, t, J = 6.5Hz, CH 2), 3.99 (2H, dd, J = 6.8,1.8Hz, CH = CH ₂ ), 4.03 (4H, t, J = 6.5 Hz, CH ₂ ), 4.19 (2H, dd, J = 14.3, 1.8 Hz, CH = CH ₂ ), 6.49 ( _{2H, dd, J = 14.3,6.8Hz,} CH = CH 2), 7.01 (4H, br d, J = 8.6Hz, Ar-H), 7.59 (4 , Brd, J = 8.7 Hz, Ar-H), 7.66-7.68 (4H, m, Ar-H), 7.72-7.74 (6H, m, Ar-H), 7 .90 (2H, d, J = 1.5 Hz, Ar-H), 7.93 (2H, d, J = 8.1 Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.4 (CH ₂ ), 14.1 (CH ₃ ), 22.6 (CH ₂ ), 24.0 (CH ₂ ), 26.0 ( _{x2) (CH 2), 29.1} (x2) (CH 2), 29.2 (CH 2), 29.3 (x3) (CH 2), 31.8 (CH 2), 33.4 (CH _{2), 68.1 (x2) (} CH 2), 86.2 (CH 2), 114.8 (CH), 121.3 (CH), 127.0 (CH), 127.3 (CH), 128.0 (CH), 128.9 (CH), 131.7 (CH), 133.0 (C), 138.8 (C), 139.4 (C), 139.5 (C), 139 0.7 (C), 147.2 (C), 152.0 (CH), 158.8 (C). MALDI-MS: 1050.6 (M ^<+> ). Elemental analysis: Expected C = 82.23, H = 9.01, measured C = 81.95, H = 8.96.

スキーム３。誘導体Ｊ８−８ＭＥＴ、Ｊ８−８ＦＵＭ、およびＪ８−８ＭＡＬの合成。 Scheme 3
First, the Williamson-ether reaction between 8-bromo-1-octanol (11) and bis-phenol (6) in a butanone-DMF solvent mixture gives compound 13 in moderate yield. Was. A mixed solvent system was utilized due to solubility issues with butanone alone. Three Steichlic esterifications under similar reaction conditions at room temperature yielded the final materials J8-8MET, J8-8FUM, and J8-8MAL in moderate yields.

Scheme 3. Synthesis of derivatives J8-8MET, J8-8FUM, and J8-8MAL.

Compound 13
_{K 2 CO 3 (1.67g, 12.1mmol} ) a compound containing a 6 (1.80g, 2.42mmol) and 1-bromo-8-octanol (11,1.27g, 6.06mmol) butanone (20 mL) And the dry DMF (20 mL) solution was stirred under nitrogen between 90 ° C. and 100 ° C. for 2 days. After completion, the salts were removed by filtration and the filtrate was concentrated under reduced pressure. The crude product is then purified by flash column chromatography (wet packing, silica gel, 30% diethyl ether in dichloromethane to 20% ethanol in dichloromethane) and dried under high vacuum for 2 days to remove residual ethanol. To give a white solid (2.06 g, 85.1%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.83 (6H, t, J = 7.0 Hz, CH ₃ ), 1.00-1.04 (4H, m, CH ₂ ); 20-1.61 (44H, m, CH ₂ ), 1.82 (4H, quint., CH ₂ ), 3.66 (4H, t, J = 6.6 Hz, CH ₂ ), 4.01 (4H , T, J = 6.4 Hz, CH ₂ ), 6.99 (4H, d, J = 8.8 Hz, Ar-H), 7.58 (4H, d, J = 8.8 Hz, Ar-H) , 7.64-7.72 (10H, m, Ar-H), 7.87-7.89 (4H, m, Ar-H). MALDI-MS: 998.6 (M ^<+> ).

J8-8MET
DCC (0.52 g, 2.50 mmol) was combined with Compound 13 (0.50 g, 0.50 mmol), methacrylic acid (0.22 g, 2.50 mmol), and DMAP (61 mg, 0.50 mmol) in dry CH ₂ Cl. ₂ (30 mL) solution was added in small portions at room temperature under a nitrogen atmosphere. The reaction mixture was stirred for 20 h, the formed DCU was filtered, the _CH 2 Cl ₂ was removed under reduced pressure. The resulting residue was purified by column chromatography (dry packing, silica gel, 80% dichloromethane in hexane) to give a white solid (0.22 g, 38.6%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.83 (6H, t, J = 6.8 Hz, CH ₃ ), 0.90 (6H, t, J = 6.8 Hz, CH ₃ ), _{1.00-1.04 (4H, m, CH 2} ), 1.20-1.51 (40H, m, CH 2), 1.70 (4H, quint., CH 2), 1.82 (4H _{, quint., CH 2),} 1.95-1.96 (6H, m, CH 3) 4.02 (4H, t, J = 6.4Hz, CH 2), 4.16 (4H, t, J = 6.8 Hz, CH ₂ ), 5.55 (2H, quint., HCH = C), 6.11 (2H, sext., J = 0.8 Hz, HCH = C), 7.00 (4H, d) , J = 8.8 Hz, Ar-H), 7.58 (4H, d, J = 8.8 Hz, Ar-H), 7.65 (4H, d) J = 8.8 Hz, Ar-H), 7.70-7.73 (6H, m, Ar-H), 7.89 (2H, d, J = 2.0 Hz, Ar-H), 7.92 (2H, d, J = 8.0 Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (CH ₃ ), 18.5 (CH ₃ ), 22.8 (CH ₂ ), 24.2 ( _{CH 2), 26.1 (CH 2} ), 26.2 (CH 2), 28.8 (CH 2), 29.3 (CH 2), 29.4 (x3) (CH 2), 32.0 _{(CH 2), 33.6 (CH} 2), 64.9 (CH 2), 68.2 (CH 2), 115.0 (CH), 121.4 (CH), 125.3 (CH), 127.2 (CH), 127.5 (CH), 128.2 (CH), 129.0 (CH), 131.9 (CH), 133.2 (CH), 136.7 (C), 139 1.0 (C), 139.5 (C), 139.7 (C), 139.8 (C), 147.4 (C), 158.9 (CO ), 167.7 (C = O). MALDI-MS: 1134.6 (M ^<+> ). Elemental analysis: expected value C = 80.38, H = 8.7, measured value C = 80.18, H = 8.53.

J8-8FUM
Drying of DCC (0.52 g, 2.50 mmol) with compound 13 (0.50 g, 0.50 mmol), mono-methyl fumarate (0.33 g, 2.50 mmol), and DMAP (61 mg, 0.50 mmol) To the CH ₂ Cl ₂ (20 mL) solution was added in small portions at room temperature under a nitrogen atmosphere. The reaction mixture was stirred for 20 h, the formed DCU was filtered and the _CH 2 Cl ₂ removed on a rotary evaporator. The resulting residue was purified by column chromatography (dry packing, silica gel, 20% ethyl acetate in hexane) to give a white solid, which was further purified by recrystallization from a DCM / ethanol layer to give a white solid. A crystalline solid (0.10 g, 16.4%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.83 (6H, t, J = 7.0 Hz, CH ₃ ), 1.00-1.04 (4H, m, CH ₂ ); _{20-1.55 (40H, m, CH 2} ), 1.70 (4H, quint., CH 2), 1.82 (4H, quint., CH 2), 3.81 (6H, s, CH 3 _{), 4.02 (4H, t,} J = 6.6Hz, CH 2), 4.21 (4H, t, J = 6.6Hz, CH 2), 6.87 (4H, s, CH = CH) , 7.00 (4H, d, J = 8.8 Hz, Ar-H), 7.58 (4H, d, J = 8.8 Hz, Ar-H), 7.65 (4H, d, J = 8). 0.4 Hz, Ar-H), 7.72 (6H, d, J = 8.0 Hz, Ar-H), 7.89 (2H, d, J = 1.6 Hz, Ar-H) , 7.92 (2H, d, J = 8.0 Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (CH ₃ ), 22.8 (CH ₂ ), 24.1 (CH ₂ ), 26.0 ( CH ₂ ), 26.1 (CH ₂ ), 28.6 (CH ₂ ), 29.2 (CH ₂ ), 29.3 (CH ₂ ), 29.4 (x2) (CH ₂ ), 32.0 _{(CH 2), 33.6 (CH} 2), 52.5 (CH 3), 65.6 (CH 3), 68.2 (CH 2), 115.0 (CH), 121.4 (CH) , 125.3 (CH), 127.2 (CH), 127.5 (CH), 128.2 (CH), 129.0 (CH), 131.9 (CH), 133.2 (CH), 133.3 (CH), 134.1 (CH), 139.0 (CH), 139.5 (C), 139.6 (C), 139 8 (C), 147.3 (C), 158.9 (CO), 165.2 (C = O), 165.6 (C = O). MALDI-MS: 1222.6 (M ^<+> ). Elemental analysis: Expected C = 76.56, H = 8.07, found C = 76.11, H = 7.99.

J8-8MAL
DCC (0.49 g, 2.35 mmol) was combined with Compound 13 (0.47 g, 0.47 mmol), ethyl hydrogen maleate (0.34 g, 2.35 mmol), and DMAP (57 mg, 0.47 mmol) in dry CH _2. To the Cl ₂ (20 mL) solution was added in small portions at room temperature under a nitrogen atmosphere. The reaction mixture was stirred for 20 h, the formed DCU was filtered, the _CH 2 Cl ₂ was removed under reduced pressure. The resulting residue was purified by column chromatography (dry packing, silica gel, 20% ethyl acetate in hexane) to give a white solid (0.20 g, 33.9%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.84 (6H, t, J = 7.0 Hz, CH ₃ ), 1.00-1.04 (4H, m, CH ₂ ); _{20-1.51 (46H, m, CH 2} ), 1.70 (4H, quint., CH 2), 1.82 (4H, quint., CH 2), 4.01 (4H, t, J = 6.6 Hz, CH ₂ ), 4.20 (4H, t, J = 6.8 Hz, CH ₂ ), 4.26 (4H, q, J = 7.2 Hz, CH ₂ ), 6.24 (4H, s, CH = CH), 6.99 (4H, d, J = 8.8 Hz, Ar-H), 7.58 (4H, d, J = 8.8 Hz, Ar-H), 7.65 (4H) , D, J = 8.4 Hz, Ar-H), 7.72 (6H, d, J = 8.4 Hz, Ar-H), 7.89-7.92 (4H, m, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (x 2) (CH ₃ ), 22.8 (CH ₂ ), 24.1 (CH ₂ ), 26 _{.0 (CH 2), 26.1 (} CH 2), 28.6 (CH 2), 29.2 (CH 2), 29.3 (CH 2), 29.4 (x2) (CH 2), _{32.0 (CH 2), 33.6 (} CH 2), 61.4 (CH 2), 65.6 (CH 3), 68.2 (CH 2), 115.0 (CH), 121.4 (CH), 125.3 (CH), 127.2 (CH), 127.5 (CH), 128.1 (CH), 129.0 (CH), 129.9 (CH), 130.0 ( CH), 131.9 (CH), 133.2 (CH), 139.0 (CH), 139.5 (C), 139.6 (C) 139.8 (C), 147.3 (C), 158.9 (CO), 165.4 (C = O), 165.5 (C = O). MALDI-MS: 1251.7 (M ^<+> ). Elemental analysis: Expected C = 76.76, H = 8.21, measured C = 76.48, H = 8.16.

スキーム４。５，５−ジオクチル−５Ｈ−ジベンゾ［ｂ，ｄ］シロール−３，７−ベンゾ［Ｃ］−１，２，５−チアジアゾール誘導体Ｋ８−８およびＫ８−８ＭＩの合成。 Scheme 4
Boronic ester (5) using catalyst Pd (PPh ₃ ) ₄ in dioxane / H ₂ O (2: 1) and commercially outsourced material 4- (7-bromobenzo [c] [1,2 , 5] Thiadiazol-4-yl) phenol (compound 14) to give bis-phenol (15) in good yield (%). Maleimide K8-8MI was synthesized in good yield (%) under conditions similar to those outlined for Scheme 8 J8-8MI. A standard Williamson-ether reaction of compound (15) with 1-bromooctane under reflux with potassium carbonate and butanone provided the final product K8-8 in excellent yield (%).

Scheme 4. Synthesis of 5,5-dioctyl-5H-dibenzo [b, d] silole-3,7-benzo [C] -1,2,5-thiadiazole derivatives K8-8 and K8-8MI.

Compound 15
Compound 14 (0.51 g, 1.67 mmol), 5,5-dioctyl-3,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H- dibenzo [b, d] silole (compound _{5,0.50g, 0.76mmol), K 2 CO} 3 (0.52g, 3.80mmol), dioxane (20 mL), and water (10 mL) all three-necked round-bottomed flask Was added. The system was degassed using nitrogen as the inert gas and using two freeze-pump-thaw cycles. Subsequently, Pd (PPh ₃ ) ₄ (44 mg, 0.04 mmol) was added and the reaction mixture was again degassed by one freeze-pump-thaw cycle and overnight at 90-100 ° C. (16 h). Heated. The reaction mixture was then acidified with 10% HCl (200 mL), then poured into a separatory funnel, the aqueous layer was extracted with diethyl ether (3 × 100 mL), and the combined organics were washed with water (300 mL) and dried ( MgSO ₄ ) and filtered. The filtrate is concentrated under reduced pressure and the crude product is purified by column chromatography (dry packing, silica gel, 30% ethyl acetate in hexane) to give a yellow powder (0.33 g, 50.8%). Was.
¹ H NMR (400 MHz, (CD ₃ ) ₂ SO): δ (ppm) 0.70 (6 H, t, J = 6.6 Hz, CH ₃ ), 1.05-1.30 (24 H, m, CH _{2 ), 1.43 (4H, quint.} , CH 2), 6.96 (4H, d, J = 8.8Hz, Ar-H), 7.88-7.92 (6H, m, Ar-H) 8.00 (2H, d, J = 7.6 Hz, Ar-H), 8.17 (4H, s, Ar-H), 8.35 (2H, s, Ar-H), 9.77 ( 2H, s, OH). MALDI-MS: 858.3 (M ^<+> ).

K8-8
_{K 2 CO 3 (80mg, 0.58mmol} ) Compound 15 (0.10g, 0.12mmol) containing and 1-bromo octane (0.11 g, 0.58 mmol) and butanone (10 mL) solution of nitrogen under reflux for 18 Stirred for hours. After completion, the salts were removed by filtration and the filtrate was concentrated under reduced pressure. The crude product was then purified by column chromatography (wet packing, silica gel, 1: 1 DCM / hexane) to give a yellow powder (0.10 g, 76.9%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.82 (6H, t, J = 6.8 Hz, CH ₃ ), 0.91 (6H, t, J = 6.8 Hz, CH ₃ ), _{1.05-1.09 (4H, m, CH 2} ), 1.21-1.54 (44H, m, CH 2), 1.85 (4H, quint., CH 2), 4.06 (4H , T, J = 6.4 Hz, CH ₂ ), 7.09 (4H, d, J = 8.8 Hz, Ar-H), 7.76 (2H, d, J = 7.2 Hz, Ar-H) , 7.85 (2H, d, J = 7.6 Hz, Ar-H), 7.95 (4H, d, J = 8.8 Hz, Ar-H), 8.05 (2H, d, J = 8) 8.0 Hz, Ar-H), 8.13 (2H, dd, J = 8.0, 1.6 Hz, Ar-H), 8.22 (2H, d, J = 1.6 Hz, Ar-H) ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (CH ₃ ), 14.3 (CH ₃ ), 22.8 (x2) (CH ₂ ), 24 _{.2 (CH 2), 26.2 (} CH 2), 29.3 (CH 2), 29.4 (x3) (CH 2), 29.5 (CH 2), 32.0 (x2) (CH ₂ ), 33.6 (CH ₂ ), 68.3 (CH ₂ ), 114.8 (CH), 121.3 (CH), 127.4 (CH), 128.0 (CH), 129.9 (C), 130.5 (CH), 131.4 (CH), 132.9 (C), 133.0 (C), 134.1 (C), 136.5 (C), 138.9 ( C), 148.1 (C), 154.4 (C), 159.6 (C). MALDI-MS: 1082.5 (M ^<+> ). Elemental analysis: Expected C = 75.37, H = 8.00, N = 5.17, found C = 75.35, H = 7.95, N = 4.99.

K8-8MI
Compound 15 (0.40 g, 0.47 mmol), compound 10 (0.50 g, 1.40 mmol), and _{K 2 CO 3 (0.32g, 2.33mmol} ) and the mixture of suspended in dry DMF (30 mL) It became cloudy. The reaction mixture was heated to 55 ° C. and stirred under nitrogen for 20 hours. Upon completion, the reaction mixture was cooled to room temperature and the salts were removed by filtration. The filtrate was evaporated under reduced pressure and the residue was redissolved in dichloromethane (100 mL) and washed with water (2 × 100 mL). The organic layer was dried (MgSO4), filtered and evaporated to dryness under reduced pressure. The crude product was then purified by flash column chromatography (50% ethyl acetate in hexane to 100% ethyl acetate) to give the protected maleimide as a light yellow solid (0.38 g, 57%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.81 (6H, t, J = 6.7 Hz, CH ₃ ), 1.05-1.09 (4H, m, CH ₂ ); _{21-1.62 (44H, m, CH 2} ), 1.80-1.87 (4H, m, CH 2), 2.84 (4H, s, CH), 3.49 (4H, t, J _{= 7.3Hz, CH 2), 4.06} (4H, t, J = 6.5Hz, CH 2), 5.28 (4H, s, CH), 6.52 (4H, s, CH = CH) , 7.08-7.10 (4H, m, Ar-H), 7.78 (2H, d, J = 7.3 Hz, Ar-H), 7.86 (2H, d, J = 7.3 Hz) , Ar-H), 7.94-7.96 (4H, m, Ar-H), 8.07 (2H, d, J = 8.2 Hz, Ar-H), 8.15 (2H, dd, J = .2Hz, Ar-H), 8.21 (2H, d, J = 1.6Hz, Ar-H).

The protected maleimide (0.27 g, 0.19 mmol) was heated at reflux in toluene (10 mL) for 16 hours to completely remove furan. The toluene was removed under reduced pressure and the crude product was purified by flash chromatography (100% dichloromethane to 4% ethyl acetate in dichloromethane) to give compound 23 as a light yellow waxy solid. This was further purified by trituration with ethanol to give the product as a light yellow solid (0.15 g, 62%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.82 (6H, t, J = 6.7 Hz, CH ₃ ), 1.06-1.10 (4H, m, CH ₂ ); _{21-1.54 (40H, m, CH 2} ), 1.58-1.65 (4H, m, CH 2), 1.81-1.88 (4H, m, CH 2), 3.54 ( _{4H, t, J = 7.3Hz,} CH 2), 4.06 (4H, t, J = 6.5Hz, CH 2), 6.07 (4H, s, CH = CH), 7.08-7 .11 (4H, t, Ar-H), 7.78 (2H, d, J = 7.5 Hz, Ar-H), 7.87 (2H, d, J = 7.5 Hz, Ar-H), 7.94-7.97 (4H, m, Ar-H), 8.07 (2H, d, J = 8.1 Hz, Ar-H), 8.15 (2H, dd, J = 8.1, 1.8 z, Ar-H), 8.21 (2H, d, J = 1.8Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.4 (CH ₂ ), 14.1 (CH ₃ ), 22.6 (CH ₂ ), 24.1 (CH ₂ ), 26.0 ( _{CH 2), 26.7 (CH 2} ), 28.5 (CH 2), 29.0 (CH 2), 29.2 (4x) (CH 2), 31.9 (CH 2), 33.5 _{(CH 2), 37.9 (CH} 2), 68.1 (CH 2), 114.7 (CH), 121.2 (CH), 127.3 (CH), 127.9 (CH), 129 .8 (C), 130.4 (CH), 131.3 (CH), 132.8 (C), 132.9 (C), 134.0 (3x) (CH, C), 136.4 ( C), 138.8 (C), 148.0 (C), 154.3 (C), 159.4 (C), 170.9 (C = O). MALDI-MS: 1272.5 (M ^<+> ). Elemental analysis: Expected C = 71.66, H = 6.96, N = 6.60, found C = 71.60, H = 6.95, N = 6.62.

スキーム５。化合物Ｌ８−８の合成。 Scheme 5
Boronic ester (5) using catalyst Pd (PPh ₃ ) ₄ in toluene / H ₂ O (2: 1) and commercially outsourced material 4-bromo-2,3,5,6-tetra Suzuki coupling reaction with methyl-4 ′-(octyloxy) -1,1′-biphenyl (compound 16) at 90 ° C. affords the final product L8-8 in good yield (%). Was.

Scheme 5. Synthesis of compound L8-8.

L8-8
4-bromo-2,3,5,6-tetramethyl-4 ′-(octyloxy) -1,1′-biphenyl (compound 16, 0.70 g, 1.67 mmol), 5,5-dioctyl-3, 7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, d] silole (Compound 5, 0.50 g, 0.76 mmol), _{K 2 CO 3 (0.52g, 3.80mmol} ), was added toluene (20 mL), and water (10 mL) all three neck round bottom flask. The system was degassed using nitrogen as the inert gas and using two freeze-pump-thaw cycles. _{Subsequently,} the addition of _{Pd (PPh 3) 4 (88mg} , 0.08mmol), the reaction mixture, one freeze - was degassed again by thaw cycles - pump. The reaction mixture was heated under nitrogen at 90 ° C. for 24 hours, poured into a separatory funnel, whereupon both water (50 ml) and toluene (50 ml) were added, and the aqueous layer was washed with toluene (20 ml) and mixed. the organic layer was washed with water (50ml), dried (MgSO _4), and filtered. The crude product was purified by column chromatography (wet packing, silica gel, 20% dichloromethane in hexane) to give a white powder, which was further purified by recrystallization from DCM / ethanol layer (0.56 g) , 68.3%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.84 (6H, t, J = 7.0 Hz, CH ₃ ), 0.91 (6H, t, J = 6.8 Hz, CH ₃ ), _{0.94-0.98 (4H, m, CH 2} ), 1.17-1.55 (50H, m, CH 2), 1.84 (4H, quint., CH 2), 2.00 (12H _{, s, Ar-CH 3)} , 2.03 (12H, s, Ar-CH 3), 4.03 (4H, t, J = 6.6Hz, CH 2), 6.98 (4H, d, J = 8.8 Hz, Ar-H), 7.08-7.13 (4H, m, Ar-H), 7.28 (2H, dd, J = 8.0, 1.6 Hz, Ar-H), 7.46 (2H, s, J = 1.6 Hz, Ar-H), 7.94 (2H, d, J = 8.0 Hz, Ar-H). ¹³ C NMR (100 MHz, CDCl ₃ ): δ (ppm) 12.5 (CH ₂ ), 14.2 (CH ₃ ), 14.3 (CH ₃ ), 22.8 (x2) (CH ₂ ), 24 2 (CH ₂ ), 26.3 (CH ₂ ), 29.2 (CH ₂ ), 29.3 (CH ₂ ), 29.4 (CH ₂ ), 29.6 (CH ₃ ), 32.0 _{(CH 2), 33.4 (CH} 3), 33.5 (CH 2), 68.1 (CH 2), 114.4 (CH), 120.7 (CH), 130.6 (CH), 131.3 (CH), 132.0 (CH), 132.5 (CH), 134.7 (C), 134.9 (C), 138.1 (C), 141.0 (C), 141 0.4 (C), 141.5 (C), 146.6 (C), 157.8 (CO). MALDI-MS: 1078.8 (M ^<+> ). Elemental analysis: Expected C = 84.54, H = 9.90, found C = 84.57, H = 9.85.

Optical Properties Luminescent materials used in OLED devices exhibit electroluminescence (EL) in the visible region of the electromagnetic spectrum. The red, green, and blue (RGB) EL colors are of fundamental importance in realizing full color OLED displays (ie, cell phones) and lighting (ie, solid white light). While excitons in EL are created by charge injection after applying an electric field, a similar process in which excitons are created by photoexcitation using, for example, UV light, is referred to as photoluminescence (PL). The EL and PL spectra are the same for the majority of the luminescent organic semiconductor materials. In order to evaluate the physical properties of the material, both absorption and fluorescence properties were investigated. Therefore, UV / Vis absorption and PL spectra of compounds in solution and in thin films were recorded (FIGS. 5a, 5b and 6a, 6b). High PL quantum yield (PLQY) in the solid state is desired, and a comparison of the material PLQY in the dilute solution state and the solid state is valuable for molecular aggregation in thin films compared to isolated molecules in the dilute solution state Information can be given. Unfortunately, the PLQY measurements of the material were beyond the scope of this work package. Samples were prepared as follows.
(A) Solution state: A sample for UV / Vis absorption and PL spectrum was put in analytical reagent grade toluene, 1 × 10 ⁻⁵ M for UV / Vis absorption spectrum, and 1 × 10 ⁵ M for PL spectrum. ^-6 was prepared by dissolving at a concentration of ^M. UV / Vis absorption spectra were recorded using a Unicam UV / Vis spectrometer and PL spectra were measured using a Jobin Yvon-spex Fluorolog. Unless otherwise stated, the excitation wavelength used for the PL spectrum was 350 nm.
(B) Thin films: Samples for UV / Vis absorption and PL spectra were prepared by spin coating from a toluene solution (analytical reagent grade) with a sample loading of 20 mg / mL. The sample was spin-coated on a quartz disk (φ = 11 mm) at a speed of 2500 rpm for 60 seconds. UV / Vis absorption spectra were recorded using a Cary 5000 UV / Vis / NIR spectrometer, and PL spectra were recorded using a Jobin Yvon-spex Fluorolog. Unless otherwise stated, the excitation wavelength used for the PL spectrum was 350 nm.

  Table 1 summarizes the absorption and light emission data for solutions and thin films of all ten compounds.

  For blue emitting compounds, J8-8 indicates a PLmax (film) equal to 408 nm, which is compared to 409 nm of the n-alkylfluorene-based analog. Regarding the green light-emitting compound, K8-8 shows a PLmax (film) of 556 nm, which is compared with 552 nm of the n-alkylfluorene-based analog. Thus, the emission properties of the dibenzo [b, d] silole-based materials, J8-8, and K8-8, are significantly similar as compared to their n-alkylfluorene counterpart materials, which indicate that 9 This suggests that replacing the carbon atom at the -position with a silicon atom has little effect on the emission properties.

Liquid Crystal Properties Refractive index anisotropy (or birefringence) is one of the distinguishing physical properties of liquid crystal materials. These properties also allow visualization of macroscopic molecular orientation. When a liquid crystal sample is placed on a glass slide with a coverslip up between two crossed polarizers under an optical microscope, various textures and birefringent colors can be observed. These textures and colors provide information about the macroscopic structure of the liquid crystal phase. Mesophase characterization was performed by both polarized light microscopy (POM) and differential scanning calorimetry (DSC). In the first example, POM was performed to obtain an approximate temperature value early in the phase transition, and the type identification of the mesophase was determined by examining the texture under a microscope. After these initial investigations, the temperature values and the designation of the mesophase were further confirmed by DSC analysis, which gave more accurate values. From POM and DSC analysis, the following properties were expected to be established: (1) melting point determination (either crystal to isotropic liquid crystal transition or crystal to liquid crystal transition), (2) transparent Point determination (transition from liquid crystal to isotropic liquid crystal), (3) size of liquid crystal transition temperature range (from melting point to clearing point) for determining liquid crystal stability, (4) identification of mesomorphic type ( (Either nematic or smectic phase), (5) crystallization tendency (and supercooling), (6) glass transition temperature (T _g ) value, and (7) thermal stability (thermal decomposition and thermal polymerization tendency). Abbreviations: Cr = crystal, N = nematic, I = isotropic, Cr-N = phase transition showing melting point transition with subsequent phase change to nematic liquid crystal state, Cr-I = isotropic liquid state A phase transition showing a melting point transition accompanied by a subsequent phase change, and NI = a phase transition showing a phase change from a nematic liquid crystal state to an isotropic liquid state. DSC thermograms can be used to show important phase transitions at relevant temperatures.

Summary of the structure in Table 2

  As can be seen from Tables 2, 3, and 4, we advantageously find that the temperature range of the liquid crystal phase of Si-containing molecules is wider than that of conventional materials such as fluorene-based materials. Was found.

表４ 構造

Table 3 Structure

Table 4 Structure

From the results of the DSC analysis, the following can be concluded: (1) K8-8MI and L8-8 are not liquid crystals but only form an isotropic liquid after melting, and (2) K8-8MI And all materials except L8-8 show a nematic liquid crystal phase, (3) dibenzo [d, b] silole-based materials show a slightly higher melting point than n-alkylfluorene analogs, and (4) dibenzo [D, b] silole-based materials show a wider crystal transition temperature range (ΔN-1) than n-alkylfluorene analogs, and (5) the side chain alkyl chains are from C ₈ H ₁₇ (octyl) to C ₆ H _When changed to ₁₃ (hexyl), the dibenzo [d, b] silole-based material exhibits a more stable 31 ° C. liquid crystal tautomeric nematic phase range compared to similar standard fluorene-based materials, (6) The The benzo [d, b] silole-benzothiadiazole material exhibits a more stable liquid crystal tautomeric nematic phase as compared to the monomorphic nematic phase exhibited by standard n-alkylfluorenes, and (7) n- The supercooling of the alkylfluorene derivative is greater than the silafluorene analog, indicating that the latter has a greater tendency to crystallize. While this can be beneficial for material purification, crystallization during device fabrication (pre-UV cure) can be detrimental and therefore less desirable for OLED device applications. However, due to the fact that the cross-linking system is a mixture of materials, crystallization should be more suppressed compared to monomolecular systems. Moreover, these problems can be neglected to some extent since crystallization in these types of rigid polymer networks is very unlikely after the formation of photocrosslinking and polymer crosslinking networks. Advantageously, dimer material, D is what is --A-S ² -B ¹ solves this problem, suppress crystallization and caused an increase in viscosity with increasing molecular weight of the compound be able to. No clearing point was detected for compound J8-8MET by POM or DSC measurements, and J8-8MET undergoes thermal polymerization after melting. Although this thermal instability is not attractive for the development of photocrosslinkable materials, J8-8MET can be an excellent candidate for a thermally crosslinkable blue emitting material.

Photocrosslinking Measurements Solution processable photocrosslinkable active materials used as hole transport and / or emissive layers in OLED devices are attractive because of their multilayer capabilities and photopatternability, A solution processing apparatus with high efficiency and resolution can be provided. The formation of a robust, insoluble, impermeable crosslinked membrane allows additional layers to be deposited from solution on top without disturbing already deposited layers. Photocrosslinkable materials allow photopatterning to achieve high resolution pixel densities. Our goal was to establish initiators for blue- and green-emitting films based on novel dibenzo [d, b] silole materials whose optimal crosslinking conditions would be identified and compared with similar alkylfluorene derivatives The goal was to develop a free photocrosslinking protocol. Photocrosslinking systems were based on electron rich (donor) -electron deficient (acceptor) type crosslinking techniques. Photocrosslinking experiments were performed under an inert atmosphere using a commercial UV-cured LED spot lamp system (385 nm, 0.5 J / cm ² ) that provides high intensity light over a small area.

  All films used in subsequent experiments were prepared using a variation of the following protocol: Materials were 1: 1 (electron rich / electron deficient) weight ratio for blue emitting material system, green emitting For the material system, thin films were prepared at a weight ratio of 5: 4: 1 (blue electron rich / blue electron deficient / green electron deficient) using a solution processing technique dissolved in toluene at a concentration of 20 mg / mL. The green-emitting material system contains 10% by weight of a green dopant followed by green-visible light to enable energy transfer from host to dopant (FRET). Thin luminescent films were prepared by spin-casting a dilute solution of the material on a circular quartz substrate (φ = 11 mm) at 2500 rpm for 60 seconds.

For the cross-linking sensitivity study of the blue-emitting system, we used the donor J8-8VE and the four acceptor materials J8-8MET, J8-8FUM, J8-8MAL, and J8-8MI shown in FIG. Were used (1: 1 weight ratio).

The following experiments were performed on thin films of the mixture prepared as described above. Photocrosslinking was performed under an inert atmosphere. Eleven identical films of the crosslinkable mixture were prepared on a quartz substrate by spin coating and a UV / Vis absorption spectrum was obtained for each sample. The samples were then exposed to different exposures of 385 nm UV light (0, 1, 2.5, 5, 7.5, 10, 15, 15 s, 20 s) at an exposure rating of 500 mJ / cm ^2. Second, 30 seconds, 40 seconds and 50 seconds). After the exposure, the UV / Vis absorption spectrum was recorded again, and it was confirmed that light deterioration due to exposure of the film to UV light did not occur. The eleven samples are then rinsed with dichloromethane (a solvent in which all uncrosslinked material readily dissolves) to remove uncrosslinked material and the UV / Vis absorption spectrum was measured last and remains after rinsing. The amount of material was determined. This process was repeated for all four crosslinkable donor-acceptor mixtures. A graph showing the sensitivity plot for the donor-acceptor crosslinkable mixture is shown in FIG. The two mixtures consisted of a 1: 1 weight ratio of donor to acceptor material (see Table 5), varied acceptor components (J8-8MET and J8-8FUM), and vinyl ether-based material J8. -8VE was kept constant and was used as the donor element in both mixtures.

Effect of Crosslinkable Groups on Luminescent Properties and Stability For OLED devices, an optimal photocrosslinking system will ideally have little effect on luminescent properties and stability. By this we mean that the effect of the crosslinkable groups and UV curing has little or no change in the CIE coordinates of the material and has little effect on the stability of the material during equipment operation. To better investigate the effect of crosslinkable groups on stability, we synthesized non-crosslinkable analogs (compounds J8-8 and K8-8).

CIE (x, y) coordinates For non-crosslinkable materials, CIE (x, y) coordinates were calculated from the PL spectra of thin films of the material spin-coated from a solution in toluene (concentration = 20 mg / mL). For the crosslinkable version, solutions were prepared as described above, and films were formed by spin coating on quartz substrates. The film was then exposed to a sufficient amount of UV light under an inert atmosphere to completely crosslink the material (25 J / cm ² ) and then rinsed with dichloromethane. The PL spectrum of the rinsed film was then recorded.

  Table 6 shows the CIE (x, y) coordinates of the biphenyl-dibenzo [d, b] silole material.

From the CIE (x, y) coordinate plot, it is clear that the crosslinkable groups affect the luminescent properties of the material. This shift is most evident with the use of a crosslinked mixture of maleimide and vinyl ether (J8-8VE / J8-8MI) and is not unexpected due to the PET quenching exhibited by the maleimide containing material. The crosslinkable system that provides the best balance between crosslinking rate and CIE (x, y) coordinates after crosslinking for blue materials is a mixture of maleate and vinyl ether (J8-8VE / J8-8MAL) because it is photocrosslinkable in energy of 15 J / cm ^2, in order to have a crosslinking CIE (x, y) coordinates after excellent x = 0.16 and y = 0.09.

The n-alkyl fluorene counterparts show similar differences in light emission due to the crosslinkable groups. As with the dibenzo [d, b] silolemaleimide mixture, the effect of PET affects the luminescent properties of the crosslinked material, resulting in CIE (x, y) coordinates of 0.19 and 0.22 (Table 7). Interestingly, the effect of the other crosslinkable groups is different between the two versions. Dibenzo [d, b] silole-based materials show significant differences between methacrylate, maleate, and fumarate crosslinkable groups, while for n-alkylfluorene analogs, the emission coordinates are x = 0.16 and y = 0. .13 group.

  Table 7 shows the CIE (x, y) coordinates of the biphenyl n-alkylfluorene material.

  The optimal CIE (x, y) coordinates for the blue material are x = 0.15, y = 0.06, which are the coordinates calculated for the non-crosslinkable dibenzo [d, b] silole material J8-8, Very close to x = 0.16, y = 0.06 (Table 6). It is also evident from FIGS. 18 and 20 that a smaller CIE (x, y) coordinate shift is observed for the dibenzo [d, b] silole material when compared to the n-alkylfluorene version. It should be noted that these conclusions were derived from CIE plots of the PL spectra of these materials, and that the results may differ from their electroluminescence (EL) spectra. It is also worth noting that when these materials are used in OLED devices, they are rarely used in neat films like those described in this section. As with our above system used for green-emitting guest-host thin films, they will be much more likely to be used with host materials. This can alter the cross-linking rate, CIE (x, y) coordinates, and material stability, so it should be further investigated.

Optical properties, photocrosslinking studies, liquid crystal action, and electrochemistry have been investigated. The data presented above demonstrate photocrosslinking of both blue and green luminescent films under inert conditions at low doses and without photodegradation. It is noteworthy that chemical synthesis is easier and lower cost than fluoroalkylfluorene-based materials. This new class of luminescent materials exhibits a nematic liquid crystal phase with a wider liquid crystal transition temperature range compared to n-alkylfluorene-like materials. Mixtures of these materials show improved photocrosslinking efficiencies in their thin films as compared to similar n-alkylfluorene materials. The CIE (x, y) coordinates of the crosslinked and non-crosslinkable blue materials also show an improvement. In addition, dibenzo [d, b] silole-based materials show almost the same HOMO level as compared to n-alkylfluorene-based materials, because the presence of added silicon atoms is almost unrelated to the oxidizing properties of the material. Suggests no effect. As expected, the electron affinity of the dibenzo [d, b] silole blue material (J8-8) was slightly increased compared to its n-alkylfluorene counterpart, which was The LUMO level of the silole-based material is slightly increased.

Claims (26)

A compound of formula (I),
^{D-S 1 -A-S 2} -B 1, formula (I)
Where:
A independently represents a conjugated chain of 1 to 30 aromatic moieties selected from the group consisting of an aromatic moiety, a heteroaromatic moiety, and an E moiety, where A is at least one E moiety Including
E is
E ¹ which is a dibenzo [d, b] silole moiety having the following structure:

E ² , which is a part of the following structure,

And E ³ , which is part of the following structure:

E is attached to S ¹ or S ² in said conjugated chain of A and optionally via a covalent bond at Y and Z;
Each R is independently selected from the group consisting of linear or branched C ₁ -C ₂₀ alkyl and C ₂ -C ₂₀ alkenyl, optionally having from 1 to 5 CH ₂ groups. Wherein each ac is replaced by oxygen, provided that the acetal, ketal, peroxide, or vinyl ether is not present in said R groups, and optionally each H bonded to C in each R group is independently May be substituted with halogen,
The X moiety is the same and is selected from the group consisting of hydrogen, linear or branched C ₁ -C ₈ alkyl, linear or branched C ₁ -C ₈ alkoxyl, and halogen; The E moiety may have the same or different X moieties,
W is either an oxygen atom or a sulfur atom;
D represents a moiety having one or more crosslinkable functional groups,
S ¹ and S ² are flexible linker groups,
B ¹ represents a moiety having one or more crosslinkable functional groups or a hydrogen atom, provided that when B ¹ represents a hydrogen atom, D represents a moiety having at least two crosslinkable functional groups. A has the following structure,
-Ar ^a- (E-Ar ^a ) _n-
Wherein each Ar ^a is independently a valence, a diradical containing an aromatic moiety, a diradical containing a heteroaromatic moiety, an E moiety, or 2-5 aromatics interconnected by a single bond. , A heteroaromatic, and / or a chain comprising an E moiety;
The compound according to claim 1, wherein n is an integer of 1 to 8. Each Ar ^a is, independently, a diradical comprising C ₆ -C ₂₂ aromatic moiety, diradical containing heteroaromatic moiety having 4 to 22 carbon atoms, bonded to one another by E moiety or a single bond, 3. The compound according to claim 2, wherein the compound is selected from the group consisting of two or three aromatic, heteroaromatic, and / or chains comprising an E moiety. The diradical containing a C ₆ -C ₂₂ aromatic moiety is 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, perylene-3,10-diyl, Perylene-2,8-diyl, perylene-3,9-diyl, and pyrene-2,7-diyl, 9,9-dialkylfluorene-2,7-diyl, 9,9-dialkylfluorene-3,6-diyl , 9- (1′-alkylidene) fluorene-2,7-diyl, 6,12-dihydro-6,6,12,12-tetraoctyl-indeno [1,2-b] fluorene-2,8-diyl, Selected from the group consisting of 6,12-dihydro-6,6,12,12-tetraoctyl-indeno [1,2-b] fluorene-3,9-diyl;
And / or said diradical containing a heteroaromatic moiety having 4 to 22 carbon atoms is 2,2'-dithiophen-5,5'-diyl, thiophen-2,5-diyl, pyrimidine-2,5- Diyl, pyridine-2,5-diyl, 1,2,4-oxazole-3,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,2,5-oxadiazole- 3,4-diyl, thieno [3,2-b] thiophene-2,5-diyl, dithieno [3,2-b: 2 ′, 3′-d] thiophene-2,6-diyl, dithieno [3, 2-b: 2 ', 3'-d] thiophen-3,7-diyl, dibenzothiophen-3,7-diyl, dibenzothiophen-4,6-diyl, and dibenzothiophen-2,8-diyl, benzo [ 1,2-b: 4,5-b '] bis [1 Benzothiophene-3,9-diyl, thiazolo [5,4-d] thiazole-2,5-diyl, oxazolo [5,4-d] oxazole-2,5-diyl, thiazolo [5,4-d] oxazole -2,5-diyl, thiazolo [4,5-d] thiazole-2,5-diyl, oxazolo [4,5-d] oxazole-2,5-diyl, thiazolo [4,5-d] oxazole-2 , 5-Diyl, 2,1,3-benzothiadiazole-4,7-diyl, 4-thien-2-yl-2,1,3-benzothiazol-7,5'-diyl, 4,7-dithiene- 2-yl-2,1,3-benzothiazole-5 ′, 5 ″ -diyl, imidazo [4,5-d] imidazole-2,5-diyl, 4-alkyl-1,2,4-triazole- 3,5-diyl, 9-alkyl carb Zol-2,7-diyl, 9-alkylcarbazole-3,6-diyl, 1,7-dialkylindolo [2,3-b] carbazole-3,9-diyl, 1,7-dialkylindolo [2 , 3-b] carbazole-2,8-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole-4,11-diyl, 2,9-dialkylcarbazolo [3,2-b] carbazole -5,12-diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-3,9-diyl, 1,7-dialkyldiindolo [3,2-b] thiophene-4,10 -Diyl, benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl, benzo [1,2-b: 5,4-b'] dithiophen-2,6-diyl, [ 1] benzothieno [3,2-b] [1] benzo Offen-2,7-diyl, benzo [1,2-d: 4,5-d '] bisoxazole-2,6-diyl, benzo [1,2-d: 5,4-d'] bisoxazole- The compound according to claim 2 or 3, wherein the compound is selected from the group consisting of 2,6-diyl and 5,5-dioxodibenzothiophene-3,7-diyl. Wherein each R group attached to the Si comprises C ₄ -C ₂₀ haloalkyl, C ₄ -C ₂₀ alkyl, or C ₄ -C ₂₀ alkenyl, and each spacer group -S ¹ and -S ² is a linear include Jo of _C 5 _{-C 14} alkyl, optionally wherein the 1-5 CH ₂ groups are each substituted by oxygen, however, acetal, ketal, peroxide or vinyl ether, is the -S ¹ or - not present in the S ² moiety, a compound according to any one of claims 1 to 4.   6. A compound according to any one of claims 1 to 5, wherein A comprises 5 to 10 E moieties and / or A represents a conjugated chain of 8 to 16 aromatic moieties.   7. A compound according to any one of claims 1 to 6, wherein A comprises at least three different aromatic moieties. B ¹ is hydrogen and D is
-B ² -S ³ -B ³ -S ^1a -AS ^2a -B ^1a ,
-S ³ (B ² ) -B ³ -S ^1a -AS ^2a -B ^1a ,
^{-S 3 (B 2) (B} 3) -S 1a -A-S 2a -B 1a or ^{-S 3 (B 2) (B} 3) a is such, D are two or more crosslinkable functional group, Represents a portion having
In the formula, B ^1a represents a moiety having a crosslinkable functional group or a hydrogen atom,
B ² and B ³ each represent a moiety having a crosslinkable functional group,
S ^1a and S ^2a are flexible linker groups,
The compound according to claim 1, wherein S ³ is a spacer group. D is the following,
^-A-S 2 -B ¹
Wherein, preferably, each of ^-A-S 2 -B ¹ in said compound are identical, the compounds according to any one of claims 1-7.   The moiety having one or more or two or more crosslinkable functional groups, wherein the crosslinkable functional group is selected from the group consisting of ethylene-based, diene, thiol, and oxetane crosslinkable functional groups. 10. The compound according to any one of 9 above.   The crosslinkable functional group is selected from the group consisting of linear and cyclic α, β-unsaturated esters, α, β-unsaturated amides, vinyl ethers, and non-conjugated diene crosslinkable groups, preferably methacrylate, ethacrylate , Ethyl maleate, ethyl fumarate, N-maleimide, vinyloxy, alkylvinyloxy, vinyl maleate, vinyl fumarate, N- (2-vinyloxymaleimide), and 1,4-pentadien-3-yl The compound according to claim 10, which is selected from: D, and, if ^present, B 1, ^{B 2,} and ^{B 3} are radiation activated crosslinking group A compound according to any one of claims 1 to 11. -S ^{1, -S} 2, ^{-S 1a} and ^{-S 2a,} is, at each occurrence, is independent of the Formula II, a compound according to any one of claims 1 to 12,
-K ₁ -R ₃ , formula (II)
Wherein R ₃ is a linear or branched C ₅ -C ₁₄ alkyl, optionally wherein said 1 to 5 CH ₂ groups are each replaced by oxygen, provided that an acetal, ketal, peroxide or vinyl ether, is the ^{-S 1,} -S 2, not present in the ^{-S 1a} or ^{-S 2a} portion,
A compound wherein K ₁ is a valence, or an ether, ester, carbonate, thioether, amine, or amide bond. −S ³ is
In each occurrence, independent of formula III,
—K ₂ —R ₄ , formula (II)
Wherein each R ₄ is independently 1 to 5 R ₅ moieties linked by a valence, ether or ester bond;
Each R ₅ moiety is independently a linear or branched C ₁ -C ₂₀ alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₆ -C ₁₆ aryl group, or a C ₄ -C ₁₅ hetero group. Each H selected from the aryl group and optionally attached to C in each R ₅ group may be independently substituted with halogen;
K ₂ is Ataishirube or ether, ester, carbonate, thioether, amine or amide bond, A compound according to any one of claims 1 to 13,.   15. The compound according to any one of claims 1 to 14, wherein the compound exhibits a liquid crystal order and is preferably nematic.   A network polymer formed by exposure to radiation of the compound according to any one of claims 1 to 15, optionally wherein said radiation is ultraviolet light.   A device comprising one or more charge transport layers and / or luminescent layers comprising a network polymer according to claim 16 or a compound according to any one of claims 1 to 15.   18. The device according to claim 17, wherein the device is an OLED device, a photovoltaic device, or a thin film transistor (TFT) device.   A hole transport layer or an electron transport layer in which the network polymer according to claim 16 or the compound according to any one of claims 1 to 15 is provided directly adjacent to the electron transport layer or the hole transport layer. Apparatus according to claim 17 or claim 18, provided respectively.   An OLED device having a luminescent layer, wherein the network polymer according to claim 16 or the compound according to any one of claims 1 to 15 forms a uniformly oriented liquid crystal structure, whereby 20. The device of claim 19, wherein said light emitting layer emits linearly polarized light.   A method of forming a device, comprising: providing a layer comprising a compound according to any one of claims 1 to 15; and selectively irradiating said layer with radiation, preferably ultraviolet radiation. 21. A method of forming a device according to any one of claims 17 to 20, comprising forming a polymer and washing away unirradiated unpolymerized compounds.   16. Providing a further layer comprising a compound according to any one of claims 1 to 15; selectively irradiating said layer with radiation, preferably ultraviolet radiation, to form a network polymer; 22. The method of claim 21, further comprising: washing out unpolymerized unpolymerized compounds.   An apparatus, comprising two or more network polymers each forming a patterned structure, wherein the structure is comprised of a material that is essentially electroluminescent, wherein the wavelength of electroluminescence emitted by one patterned structure is 23. The device obtained by the method according to claim 22, wherein the wavelength is different from the wavelength of the electroluminescence emitted by at least one other patterned structure. Use of a compound according to formula IV,

Wherein Lg is a halogen atom or a borate leaving group, preferably Lg is bromine;
Each R is independently selected from the group consisting of linear or branched C ₁ -C ₂₀ alkyl and C ₂ -C ₂₀ alkenyl, optionally having from 1 to 5 CH ₂ groups. Wherein each ac is replaced by oxygen, provided that the acetal, ketal, peroxide, or vinyl ether is not present in said R groups, and optionally each H bonded to C in each R group is independently May be substituted with halogen,
The X moiety is the same and is selected from the group consisting of hydrogen, linear or branched C ₁ -C ₈ alkyl, linear or branched C ₁ -C ₈ alkoxyl, and halogen;
Compounds of formula IV may provide one or more E ¹ portion, for synthesizing a compound according to any one of claims 1 to 15, using the compound. Use of a compound according to formula V,

Wherein R ₁ and R ₂ are independently selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl, or C ₅ -C ₉ heteroaryl;
L ₁ and L ₂ are independently selected from a leaving group, optionally Cl, Br, I, O-tosyl, O-mesyl, or O-trifuryl;
m and s are each independently an integer selected from 1 to 10,
The synthesis comprises alkylating with phenolic oxygen and a compound of formula V;
Compounds of formula V may provide one or more S ³ portion, for synthesizing a compound according to any one of claims 1 to 15, using the compound. The use according to claim 25, wherein the compound according to formula V is diethyl-2,5-di (bromohexyl) oxyterephthalate.

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